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

DOE Office of Scientific and Technical Information (OSTI.GOV)

King, Sean W., E-mail: sean.king@intel.com; Tanaka, Satoru; Davis, Robert F.

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 desorptionmore » (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.« less

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.

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.

Laboratory Studies of Alkali Components in Tenuous Planetary Atmospheres

NASA Astrophysics Data System (ADS)

Yakshinskiy, B. V.

2004-05-01

We report on studies performed at the Laboratory for Surface Modification of Rutgers University and focused on the origin of alkali vapors (Na, K) in the tenuous atmospheres of the planet Mercury, the Moon, and Jupiter's icy satellite Europa [1, 2]; we also address the question why alkaline-earth metals (Mg, Ca) are less abundant in the atmospheres. A variety of ultrahigh-vacuum surface science techniques are used, including X-ray Photoelectron Spectroscopy (XPS), Low-Energy Ion Scattering (LEIS), Thermal Programmed Desorption (TPD), Electron- and Photon-Stimulated Desorption (ESD and PSD), Surface Ionization (SI). Measurements have been made on different samples, including the model mineral binary oxide SiO2 that simulates lunar silicates, and a lunar sample obtained from NASA. Desorption induced by electronic excitations (mainly PSD) rather than by thermal processes is found to be the dominant source process on the lunar surface. The flux at the lunar surface of ultraviolet photons from the Sun is adequate to insure that PSD of sodium contributes substantially to the Moon's atmosphere. A model based on irradiation-induced charge-transfer is proposed to explain the desorption process. There is a strong temperature-dependence of Na ESD and PSD signals from a lunar sample, under conditions where the Na surface coverage is constant and thermal desorption is negligible [3]. On Mercury solar heating of the surface is high enough that thermal desorption will also be a potential source of atmospheric sodium. Ion bombardment of the lunar sample causes both the sputtering of alkali atoms into vacuum and implantation into the sample bulk. In the future we outline the use a novel method, Nuclear Resonance Profiling (NRP) to study the diffusion of alkalis through model minerals, ices, and lunar samples; these measurements would provide additional information to understand the replenishment of Na at the surface of the Moon, Mercury and Europa. We also describe a new detector that we will use to search for desorption of alkaline-earth atoms. [1] T.E. Madey, R.E. Johnson, T.M. Orlando, Surf. Sci. 500 (2002) 838. [2] B.V. Yakshinskiy, T.E. Madey, Surf. Sci. 528 (2003) 54. [3] B.V. Yakshinskiy, T.E. Madey, Icarus 168 (2004) 53.

In-injection port thermal desorption for explosives trace evidence analysis.

PubMed

Sigman, M E; Ma, C Y

1999-10-01

A gas chromatographic method utilizing thermal desorption of a dry surface wipe for the analysis of explosives trace chemical evidence has been developed and validated using electron capture and negative ion chemical ionization mass spectrometric detection. Thermal desorption was performed within a split/splitless injection port with minimal instrument modification. Surface-abraded Teflon tubing provided the solid support for sample collection and desorption. Performance was characterized by desorption efficiency, reproducibility, linearity of the calibration, and method detection and quantitation limits. Method validation was performed with a series of dinitrotoluenes, trinitrotoluene, two nitroester explosives, and one nitramine explosive. The method was applied to the sampling of a single piece of debris from an explosion containing trinitrotoluene.

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

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.

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

PubMed

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

2006-03-07

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

An assessment of the environmental fate of mercury species in highly polluted brownfields by means of thermal desorption.

PubMed

Rumayor, M; Gallego, J R; Rodríguez-Valdés, E; Díaz-Somoano, M

2017-03-05

High contents of mercury (Hg) have been found in old mining-metallurgy sites occurring a widespread contamination and degradation of the land. The ability to identify the Hg species present in these areas is essential to clarify fate of Hg and its bioavailability and additionally, to be able to parameterize remediation techniques based on thermal desorption in order to carry out a full-scale decontamination of the land. This study has proven the usefulness of a thermal programmed desorption procedure (Hg-TPD) for identifying Hg species in contaminated samples related to mining-metallurgy activities. Hg bound to organic matter (Hg-OM) and to pyrite (Hg-FeS 2 ), HgS red, HgCl 2 , Hg 0 and HgO were identified in most of waste samples. The absence of mobile Hg species in soils and sediments showed both its re-emission to the atmosphere (Hg 0 ) or of its oxidation and lixiviation (HgO and HgCl 2 ) over the years. The results have demonstrated that most of these polluted solids can be remediated by thermal treatment at temperatures ranging between 150 and 600°C. The study evidence that Hg-TPD is useful either for parameterizing a thermal remediation or for identifying the evolution pathways of Hg species in different environmental compartments and in general, for any environmental remediation treatment. Copyright © 2016 Elsevier B.V. All rights reserved.

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

PubMed

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

2015-11-28

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

Spatially resolved thermal desorption/ionization coupled with mass spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 themore » 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.« less

Formation of a knudsen layer in electronically induced desorption

NASA Astrophysics Data System (ADS)

Sibold, D.; Urbassek, H. M.

1992-10-01

For intense desorption fluxes, particles desorbed by electronic transitions (DIET) from a surface into a vacuum may thermalize in the gas cloud forming above the surface. In immediate vicinity to the surface, however, a non-equilibrium layer (the Knudsen layer) exists which separates the recently desorbed, non-thermal particles from the thermalized gas cloud. We investigate by Monte Carlo computer simulation the time it takes to form a Knudsen layer, and its properties. It is found that a Knudsen layer, and thus also a thermalized gas cloud, is formed after around 200 mean free flight times of the desorbing particles, corresponding to a desorption of 20 monolayers. At the end of the Knudsen layer, the gas density will be higher, and the flow velocity and temperature smaller, than literature values indicate for thermal desorption. These data are of fundamental interest for the modeling of gas-kinetic and gas-dynamic effects in DIET.

DOE Office of Scientific and Technical Information (OSTI.GOV)

King, Sean W., E-mail: sean.king@intel.com; Davis, Robert F.; Carter, Richard J.

The desorption kinetics of molecular hydrogen (H{sub 2}) from silicon (001) surfaces exposed to aqueous hydrogen fluoride and remote hydrogen plasmas were examined using temperature programmed desorption. Multiple H{sub 2} desorption states were observed and attributed to surface monohydride (SiH), di/trihydride (SiH{sub 2/3}), and hydroxide (SiOH) species, subsurface hydrogen trapped at defects, and hydrogen evolved during the desorption of surface oxides. The observed surface hydride species were dependent on the surface temperature during hydrogen plasma exposure with mono, di, and trihydride species being observed after low temperature exposure (150 °C), while predominantly monohydride species were observed after higher temperature exposure (450 °C).more » The ratio of surface versus subsurface H{sub 2} desorption was also found to be dependent on the substrate temperature with 150 °C remote hydrogen plasma exposure generally leading to more H{sub 2} evolved from subsurface states and 450 °C exposure leading to more H{sub 2} desorption from surface SiH{sub x} species. Additional surface desorption states were observed, which were attributed to H{sub 2} desorption from Si (111) facets formed as a result of surface etching by the remote hydrogen plasma or aqueous hydrogen fluoride treatment. The kinetics of surface H{sub 2} desorption were found to be in excellent agreement with prior investigations of silicon surfaces exposed to thermally generated atomic hydrogen.« less

Detection of Nonvolatile Inorganic Oxidizer-Based Explosives from Wipe Collections by Infrared Thermal Desorption-Direct Analysis in Real Time Mass Spectrometry.

PubMed

Forbes, Thomas P; Sisco, Edward; Staymates, Matthew

2018-05-07

Infrared thermal desorption (IRTD) was coupled with direct analysis in real time mass spectrometry (DART-MS) for the detection of both inorganic and organic explosives from wipe collected samples. This platform generated discrete and rapid heating rates that allowed volatile and semivolatile organic explosives to thermally desorb at relatively lower temperatures, while still achieving elevated temperatures required to desorb nonvolatile inorganic oxidizer-based explosives. IRTD-DART-MS demonstrated the thermal desorption and detection of refractory potassium chlorate and potassium perchlorate oxidizers, compounds difficult to desorb with traditional moderate-temperature resistance-based thermal desorbers. Nanogram to sub-nanogram sensitivities were established for analysis of a range of organic and inorganic oxidizer-based explosive compounds, with further enhancement limited by the thermal properties of the most common commercial wipe materials. Detailed investigations and high-speed visualization revealed conduction from the heated glass-mica base plate as the dominant process for heating of the wipe and analyte materials, resulting in thermal desorption through boiling, aerosolization, and vaporization of samples. The thermal desorption and ionization characteristics of the IRTD-DART technique resulted in optimal sensitivity for the formation of nitrate adducts with both organic and inorganic species. The IRTD-DART-MS coupling and IRTD in general offer promising explosive detection capabilities to the defense, security, and law enforcement arenas.

The influence of dislocation and hydrogen on thermal helium desorption behavior in Fe9Cr alloys

NASA Astrophysics Data System (ADS)

Zhu, Te; Jin, Shuoxue; Gong, Yihao; Lu, Eryang; Song, Ligang; Xu, Qiu; Guo, Liping; Cao, Xingzhong; Wang, Baoyi

2017-11-01

Transmutation helium may causes serious embrittlement which is considered to be due to helium from clustering as a bubble in materials. Suppression of transmutation helium can be achieved by introducing trapping sites such as dislocations and impurities in materials. Here, effects of intentionally-induced dislocations and hydrogen on helium migrate and release behaviors were investigated using thermal desorption spectrometry (TDS) technique applied to well-annealed and cold-worked Fe9Cr alloys irradiated by energetic helium/hydrogen ions. Synchronous desorption of helium and hydrogen was observed, and the microstructure states during helium release at different temperatures were analyzed. High thermally stable HenD type complexes formed in cold-worked specimens, resulting in the retardation of helium migration and release. The existence of hydrogen will strongly affect the thermal helium desorption which could be reflected in the TDS spectrum. It was confirmed that hydrogen retained in the specimens can result in obvious delay of helium desorption.

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.

Comparison of a disposable sorptive sampler with thermal desorption in a gas chromatographic inlet, or in a dedicated thermal desorber, to conventional stir bar sorptive extraction-thermal desorption for the determination of micropollutants in water.

PubMed

Wooding, Madelien; Rohwer, Egmont R; Naudé, Yvette

2017-09-01

The presence of micropollutants in the aquatic environment is a worldwide environmental concern. The diversity of micropollutants and the low concentration levels at which they may occur in the aquatic environment have greatly complicated the analysis and detection of these chemicals. Two sorptive extraction samplers and two thermal desorption methods for the detection of micropollutants in water were compared. A low-cost, disposable, in-house made sorptive extraction sampler was compared to SBSE using a commercial Twister sorptive sampler. Both samplers consisted of polydimethylsiloxane (PDMS) as a sorptive medium to concentrate micropollutants. Direct thermal desorption of the disposable samplers in the inlet of a GC was compared to conventional thermal desorption using a commercial thermal desorber system (TDS). Comprehensive gas chromatography coupled to time-of-flight mass spectrometry (GC × GC-TOFMS) was used for compound separation and identification. Ten micropollutants, representing a range of heterogeneous compounds, were selected to evaluate the performance of the methods. The in-house constructed sampler, with its associated benefits of low-cost and disposability, gave results comparable to commercial SBSE. Direct thermal desorption of the disposable sampler in the inlet of a GC eliminated the need for expensive consumable cryogenics and total analysis time was greatly reduced as a lengthy desorption temperature programme was not required. Limits of detection for the methods ranged from 0.0010 ng L -1 to 0.19 ng L -1 . For most compounds, the mean (n = 3) recoveries ranged from 85% to 129% and the % relative standard deviation (% RSD) ranged from 1% to 58% with the majority of the analytes having a %RSD of less than 30%. Copyright © 2017 Elsevier B.V. All rights reserved.

Assessment and Prediction of Biostabilization of Polycyclic Aromatic Hydrocarbons (PAHs) in Sediments

DTIC Science & Technology

2001-01-01

32. Gratwohl, P. Envioron . Sci. Techno!. 24, 1687-1693 (1990). 33. EPA watch: Corps, EPA agree on sediment quality criteria. Envioron . Sci. Techno...33. 192A-193A (1999). 34. Renner, R. Envioron . Sci. Techno!. 32, 306A (1998). Abstract Section 4 Thermal Program Desorption of PAHs From Mineral

Thermal desorption of dimethyl methylphosphonate from MoO 3

DOE PAGES

Head, Ashley R.; Tang, Xin; Hicks, Zachary; ...

2017-03-03

Organophosphonates are used as chemical warfare agents, pesticides, and corrosion inhibitors. New materials for the sorption, detection, and decomposition of these compounds are urgently needed. To facilitate materials and application innovation, a better understanding of the interactions between organophosphonates and surfaces is required. To this end, we have used diffuse reflectance infrared Fourier transform spectroscopy to investigate the adsorption geometry of dimethyl methylphosphonate (DMMP) on MoO 3, a material used in chemical warfare agent filtration devices. We further applied ambient pressure X-ray photoelectron spectroscopy and temperature programmed desorption to study the adsorption and desorption of DMMP. While DMMP adsorbs intactmore » on MoO 3, desorption depends on coverage and partial pressure. At low coverages under UHV conditions, the intact adsorption is reversible. Decomposition occurs with higher coverages, as evidenced by PCH x and PO x decomposition products on the MoO 3 surface. Heating under mTorr partial pressures of DMMP results in product accumulation.« less

Expanding the capability of reaction-diffusion codes using pseudo traps and temperature partitioning: Applied to hydrogen uptake and release from tungsten

DOE Office of Scientific and Technical Information (OSTI.GOV)

Simmonds, M. J.; Yu, J. H.; Wang, Y. Q.

Simulating the implantation and thermal desorption evolution in a reaction-diffusion model requires solving a set of coupled differential equations that describe the trapping and release of atomic species in Plasma Facing Materials (PFMs). These fundamental equations are well outlined by the Tritium Migration Analysis Program (TMAP) which can model systems with no more than three active traps per atomic species. To overcome this limitation, we have developed a Pseudo Trap and Temperature Partition (PTTP) scheme allowing us to lump multiple inactive traps into one pseudo trap, simplifying the system of equations to be solved. For all temperatures, we show themore » trapping of atoms from solute is exactly accounted for when using a pseudo trap. However, a single effective pseudo trap energy can not well replicate the release from multiple traps, each with its own detrapping energy. However, atoms held in a high energy trap will remain trapped at relatively low temperatures, and thus there is a temperature range in which release from high energy traps is effectively inactive. By partitioning the temperature range into segments, a pseudo trap can be defined for each segment to account for multiple high energy traps that are actively trapping but are effectively not releasing atoms. With increasing temperature, as in controlled thermal desorption, the lowest energy trap is nearly emptied and can be removed from the set of coupled equations, while the next higher energy trap becomes an actively releasing trap. Each segment is thus calculated sequentially, with the last time step of a given segment solution being used as an initial input for the next segment as only the pseudo and actively releasing traps are modeled. This PTTP scheme is then applied to experimental thermal desorption data for tungsten (W) samples damaged with heavy ions, which display six distinct release peaks during thermal desorption. Without modifying the TMAP7 source code the PTTP scheme is shown to successfully model the D retention in all six traps. In conclusion, we demonstrate the full reconstruction from the plasma implantation phase through the controlled thermal desorption phase with detrapping energies near 0.9, 1.1, 1.4, 1.7, 1.9 and 2.1 eV for a W sample damaged at room temperature.« less

Expanding the capability of reaction-diffusion codes using pseudo traps and temperature partitioning: Applied to hydrogen uptake and release from tungsten

DOE PAGES

Simmonds, M. J.; Yu, J. H.; Wang, Y. Q.; ...

2018-06-04

Simulating the implantation and thermal desorption evolution in a reaction-diffusion model requires solving a set of coupled differential equations that describe the trapping and release of atomic species in Plasma Facing Materials (PFMs). These fundamental equations are well outlined by the Tritium Migration Analysis Program (TMAP) which can model systems with no more than three active traps per atomic species. To overcome this limitation, we have developed a Pseudo Trap and Temperature Partition (PTTP) scheme allowing us to lump multiple inactive traps into one pseudo trap, simplifying the system of equations to be solved. For all temperatures, we show themore » trapping of atoms from solute is exactly accounted for when using a pseudo trap. However, a single effective pseudo trap energy can not well replicate the release from multiple traps, each with its own detrapping energy. However, atoms held in a high energy trap will remain trapped at relatively low temperatures, and thus there is a temperature range in which release from high energy traps is effectively inactive. By partitioning the temperature range into segments, a pseudo trap can be defined for each segment to account for multiple high energy traps that are actively trapping but are effectively not releasing atoms. With increasing temperature, as in controlled thermal desorption, the lowest energy trap is nearly emptied and can be removed from the set of coupled equations, while the next higher energy trap becomes an actively releasing trap. Each segment is thus calculated sequentially, with the last time step of a given segment solution being used as an initial input for the next segment as only the pseudo and actively releasing traps are modeled. This PTTP scheme is then applied to experimental thermal desorption data for tungsten (W) samples damaged with heavy ions, which display six distinct release peaks during thermal desorption. Without modifying the TMAP7 source code the PTTP scheme is shown to successfully model the D retention in all six traps. In conclusion, we demonstrate the full reconstruction from the plasma implantation phase through the controlled thermal desorption phase with detrapping energies near 0.9, 1.1, 1.4, 1.7, 1.9 and 2.1 eV for a W sample damaged at room temperature.« less

Thermal coupling potential of Solid Oxide Fuel Cells with metal hydride tanks: Thermodynamic and design considerations towards integrated systems

NASA Astrophysics Data System (ADS)

Yiotis, Andreas G.; Kainourgiakis, Michael E.; Kosmidis, Lefteris I.; Charalambopoulou, Georgia C.; Stubos, Athanassios K.

2014-12-01

We study the thermal coupling potential between a high temperature metal hydride (MH) tank and a Solid Oxide Fuel Cell (SOFC) aiming towards the design of an efficient integrated system, where the thermal power produced during normal SOFC operation is redirected towards the MH tank in order to maintain H2 desorption without the use of external heating sources. Based on principles of thermodynamics, we calculate the energy balance in the SOFC/MH system and derive analytical expressions for both the thermal power produced during SOFC operation and the corresponding thermal power required for H2 desorption, as a function of the operating temperature, efficiency and fuel utilization ratio in the SOFC, and the MH enthalpy of desorption in the tank. Based on these calculations, we propose an integrated SOFC/MH design where heat is transferred primarily by radiation to the tank in order to maintain steady-state desorption conditions. We develop a mathematical model for this particular design that accounts for heat/mass transfer and desorption kinetics in the tank, and solve for the dynamics of the system assuming MgH2 as a storage material. Our results focus primarily on tank operating conditions, such as pressure, temperature and H2 saturation profiles vs operation time.

Methanol ice co-desorption as a mechanism to explain cold methanol in the gas-phase

NASA Astrophysics Data System (ADS)

Ligterink, N. F. W.; Walsh, C.; Bhuin, R. G.; Vissapragada, S.; van Scheltinga, J. Terwisscha; Linnartz, H.

2018-05-01

Context. Methanol is formed via surface reactions on icy dust grains. Methanol is also detected in the gas-phase at temperatures below its thermal desorption temperature and at levels higher than can be explained by pure gas-phase chemistry. The process that controls the transition from solid state to gas-phase methanol in cold environments is not understood. Aims: The goal of this work is to investigate whether thermal CO desorption provides an indirect pathway for methanol to co-desorb at low temperatures. Methods: Mixed CH3OH:CO/CH4 ices were heated under ultra-high vacuum conditions and ice contents are traced using RAIRS (reflection absorption IR spectroscopy), while desorbing species were detected mass spectrometrically. An updated gas-grain chemical network was used to test the impact of the results of these experiments. The physical model used is applicable for TW Hya, a protoplanetary disk in which cold gas-phase methanol has recently been detected. Results: Methanol release together with thermal CO desorption is found to be an ineffective process in the experiments, resulting in an upper limit of ≤ 7.3 × 10-7 CH3OH molecules per CO molecule over all ice mixtures considered. Chemical modelling based on the upper limits shows that co-desorption rates as low as 10-6 CH3OH molecules per CO molecule are high enough to release substantial amounts of methanol to the gas-phase at and around the location of the CO thermal desorption front in a protoplanetary disk. The impact of thermal co-desorption of CH3OH with CO as a grain-gas bridge mechanism is compared with that of UV induced photodesorption and chemisorption.

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.

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

PubMed

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

2010-06-15

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

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

2015-11-07

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.

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 ...

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 advancedmore » 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.« less

PCDD/F formation during thermal desorption of p,p'-DDT contaminated soil.

PubMed

Zhao, Zhonghua; Ni, Mingjiang; Li, Xiaodong; Buekens, Alfons; Yan, Jianhua

2017-05-01

Thermal treatment of polychlorinated biphenyls (PCB) contaminated soil was shown in earlier work to generate polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF). In this study, the PCDD/F were studied arising during the remediation of p,p'-DDT contaminated soil by thermal desorption. Three kinds of soil (sandy, clayey and lateritic soil) were tested to investigate the effect of soil texture on PCDD/F formation. Those soils were artificially polluted with p,p'-DDT, obtaining a concentration level of 100 mg/kg. Thermal desorption experiments were conducted for 10 min at 300 °C in an air atmosphere. The total concentration of PCDD/F generated for three soils were 331, 803 and 865 ng/kg, respectively, and TeCDD and TeCDF were dominant among all PCDD/F congeners. After thermal desorption, the total amount of PCDD/F generated both in soil and in off-gas correlated positively with the amount of DDT added to soil. In addition, a possible pathway of the formation of PCDD/F was presented.

Laser desorption of explosives as a way to create an effective non-contact sampling device

NASA Astrophysics Data System (ADS)

Akmalov, Artem E.; Chistyakov, Alexander A.; Kotkovskii, Gennadii E.

2015-10-01

Comparison of desorption effectiveness of Nd3+:YAG nanosecond laser sources (λ=266, 354, 532 nm) has been carried out to investigate a possibility of creating a non-contact sampling device for detectors of explosives based on principles of ion mobility spectrometry (IMS) and field asymmetric ion mobility spectrometry (FAIMS). The results of mass spectrometric study of laser desorption of nitroamine, nitrate ester and nitroaromatic compounds from a quartz substrate are presented. It is shown that irradiation of adsorbed layers of studied samples by a single pulse of non-resonant laser radiation (λ=532 nm) leads to efficient desorption at laser intensity 107 W/cm2 and above. Excitation of the first singlet state of nitro compounds by resonant radiation (λ=354 nm) provides heating of adsorbed layers and thermal desorption. A strongly non-equilibrium (non-thermal) dissociation process is developed when the second singlet state of nitroaromatic molecules is excited by radiation at λ=266 nm, along with thermal desorption. It is shown that Nd3+: YAG laser with wavelength λ=266 nm, pulse duration 5-10 ns, intensity 107-109 W/cm2 is the most effective source for creation a non-contact sampling device based on desorption of explosives from surfaces.

Sorption of hydrogen by silica aerogel at low-temperatures

NASA Astrophysics Data System (ADS)

Dolbin, A. V.; Khlistyuck, M. V.; Esel'son, V. B.; Gavrilko, V. G.; Vinnikov, N. A.; Basnukaeva, R. M.; Martsenuk, V. E.; Veselova, N. V.; Kaliuzhnyi, I. A.; Storozhko, A. V.

2018-02-01

The programmed thermal desorption method is used at temperatures of 7-95 K to study the sorption and subsequent desorption of hydrogen by a sample of silica aerogel. Physical sorption of hydrogen owing to the weak van-der-Waals interaction of hydrogen molecules with the silicon dioxide walls of the pores of the sample was observed over the entire temperature range. The total capacity of the aerogel sample for hydrogen was ˜1.5 mass %. It was found that when the sample temperature was lowered from 95 to 60 K, the characteristic sorption times for hydrogen by the silica aerogel increase; this is typical of thermally activated diffusion (Ea ≈ 408 K). For temperatures of 15-45 K the characteristic H2 sorption times depended weakly on temperature, presumably because of the predominance of a tunnel mechanism for diffusion over thermally activated diffusion. Below 15 K the characteristic sorption times increase somewhat as the temperature is lowered; this may be explained by the formation of a monolayer of H2 molecules on the surface of the aerogel grains.

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...

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...

Distribution and removal of organochlorine pesticides in waste clay bricks from an abandoned manufacturing plant using low-temperature thermal desorption technology.

PubMed

Cong, Xin; Li, Fasheng; Kelly, Ryan M; Xue, Nandong

2018-04-01

The distribution of pollutants in waste clay bricks from an organochlorine pesticide-contaminated site was investigated, and removal of the pollutants using a thermal desorption technology was studied. The results showed that the contents of HCHs in both the surface and the inner layer of the bricks were slightly higher than those of DDTs. The total pore volume of the bricks was 37.7 to 41.6% with an increase from external to internal surfaces. The removal efficiency by thermal treatment was within 62 to 83% for HCHs and DDTs in bricks when the temperature was raised from 200 to 250 °C after 1 h. HCHs were more easily removed than DDTs with a higher temperature. Either intraparticle or surface diffusion controls the desorption processes of pollutants in bricks. It was feasible to use the polluted bricks after removal of the pollutants by low-temperature thermal desorption technology.

Evaluation of active sampling strategies for the determination of 1,3-butadiene in air

NASA Astrophysics Data System (ADS)

Vallecillos, Laura; Maceira, Alba; Marcé, Rosa Maria; Borrull, Francesc

2018-03-01

Two analytical methods for determining levels of 1,3-butadiene in urban and industrial atmospheres were evaluated in this study. Both methods are extensively used for determining the concentration of volatile organic compounds in the atmosphere and involve collecting samples by active adsorptive enrichment on solid sorbents. The first method uses activated charcoal as the sorbent and involves liquid desorption with carbon disulfide. The second involves the use of a multi-sorbent bed with two graphitised carbons and a carbon molecular sieve as the sorbent, with thermal desorption. Special attention was paid to the optimization of the sampling procedure through the study of sample volume, the stability of 1,3-butadiene once inside the sampling tube and the humidity effect. In the end, the thermal desorption method showed better repeatability and limits of detection and quantification for 1,3-butadiene than the liquid desorption method, which makes the thermal desorption method more suitable for analysing air samples from both industrial and urban atmospheres. However, sampling must be performed with a pre-tube filled with a drying agent to prevent the loss of the adsorption capacity of the solid adsorbent caused by water vapour. The thermal desorption method has successfully been applied to determine of 1,3-butadiene inside a 1,3-butadiene production plant and at three locations in the vicinity of the same plant.

Broad spectrum infrared thermal desorption of wipe-based explosive and narcotic samples for trace mass spectrometric detection.

PubMed

Forbes, Thomas P; Staymates, Matthew; Sisco, Edward

2017-08-07

Wipe collected analytes were thermally desorbed using broad spectrum near infrared heating for mass spectrometric detection. Employing a twin tube filament-based infrared emitter, rapid and efficiently powered thermal desorption and detection of nanogram levels of explosives and narcotics was demonstrated. The infrared thermal desorption (IRTD) platform developed here used multi-mode heating (direct radiation and secondary conduction from substrate and subsequent convection from air) and a temperature ramp to efficiently desorb analytes with vapor pressures across eight orders of magnitude. The wipe substrate experienced heating rates up to (85 ± 2) °C s -1 with a time constant of (3.9 ± 0.2) s for 100% power emission. The detection of trace analytes was also demonstrated from complex mixtures, including plastic-bonded explosives and exogenous narcotics, explosives, and metabolites from collected artificial latent fingerprints. Manipulation of the emission power and duration directly controlled the heating rate and maximum temperature, enabling differential thermal desorption and a level of upstream separation for enhanced specificity. Transitioning from 100% power and 5 s emission duration to 25% power and 30 s emission enabled an order of magnitude increase in the temporal separation (single seconds to tens of seconds) of the desorption of volatile and semi-volatile species within a collected fingerprint. This mode of operation reduced local gas-phase concentrations, reducing matrix effects experienced with high concentration mixtures. IRTD provides a unique platform for the desorption of trace analytes from wipe collections, an area of importance to the security sector, transportation agencies, and customs and border protection.

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

PubMed Central

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

2010-01-01

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. PMID:20644659

Desorption kinetics of {H}/{Mo(211) }

NASA Astrophysics Data System (ADS)

Lopinski, G. P.; Prybyla, J. A.; Estrup, P. J.

1994-08-01

The desorption kinetics of the {H}/{Mo(211) } chemisorption system were studied by thermal desorption and measurement of adsorption isobars. Analysis of the steady-state measurements permits the independent determination of the desorption energy ( Ed) and prefactor ( v). These quantities are found to depend strongly on coverage, with ( Ed) varying continuously from 145 {kJ}/{mol} at low coverage to 65 {kJ}/{mol} near saturation. Three regions of hydrogen adsorption are clearly indicated by the isobars as well as the thermal desorption traces. These regions can be correlated with structural changes observed previously with HREELS and LEED. The coverage dependence of the kinetic parameters is attributed to hydrogen-induced local distortions of the substrate structure. By relating the desorption energy to the isosteric heat the partial molar entropy is also extracted from the data and indicates localized adsorption as well as significant adsorbate-induced changes in the substrate degrees of freedom.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guterl, Jerome, E-mail: jguterl@ucsd.edu; Smirnov, R. D.; Krasheninnikov, S. I.

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 samplesmore » 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.« less

Thermal desorption of formamide and methylamine from graphite and amorphous water ice surfaces

NASA Astrophysics Data System (ADS)

Chaabouni, H.; Diana, S.; Nguyen, T.; Dulieu, F.

2018-04-01

Context. Formamide (NH2CHO) and methylamine (CH3NH2) are known to be the most abundant amine-containing molecules in many astrophysical environments. The presence of these molecules in the gas phase may result from thermal desorption of interstellar ices. Aims: The aim of this work is to determine the values of the desorption energies of formamide and methylamine from analogues of interstellar dust grain surfaces and to understand their interaction with water ice. Methods: Temperature programmed desorption (TPD) experiments of formamide and methylamine ices were performed in the sub-monolayer and monolayer regimes on graphite (HOPG) and non-porous amorphous solid water (np-ASW) ice surfaces at temperatures 40-240 K. The desorption energy distributions of these two molecules were calculated from TPD measurements using a set of independent Polanyi-Wigner equations. Results: The maximum of the desorption of formamide from both graphite and ASW ice surfaces occurs at 176 K after the desorption of H2O molecules, whereas the desorption profile of methylamine depends strongly on the substrate. Solid methylamine starts to desorb below 100 K from the graphite surface. Its desorption from the water ice surface occurs after 120 K and stops during the water ice sublimation around 150 K. It continues to desorb from the graphite surface at temperatures higher than160 K. Conclusions: More than 95% of solid NH2CHO diffuses through the np-ASW ice surface towards the graphitic substrate and is released into the gas phase with a desorption energy distribution Edes = 7460-9380 K, which is measured with the best-fit pre-exponential factor A = 1018 s-1. However, the desorption energy distribution of methylamine from the np-ASW ice surface (Edes = 3850-8420 K) is measured with the best-fit pre-exponential factor A = 1012 s-1. A fraction of solid methylamine monolayer of roughly 0.15 diffuses through the water ice surface towards the HOPG substrate. This small amount of methylamine desorbs later with higher binding energies (5050-8420 K) that exceed that of the crystalline water ice (Edes = 4930 K), which is calculated with the same pre-exponential factor A = 1012 s-1. The best wetting ability of methylamine compared to H2O molecules makes CH3NH2 molecules a refractory species for low coverage. Other binding energies of astrophysical relevant molecules are gathered and compared, but we could not link the chemical functional groups (amino, methyl, hydroxyl, and carbonyl) with the binding energy properties. Implications of these high binding energies are discussed.

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

EPA Science Inventory

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

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

EPA Science Inventory

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

Weak interactions between water and clathrate-forming gases at low pressures

DOE PAGES

Thürmer, Konrad; Yuan, Chunqing; Kimmel, Greg A.; ...

2015-07-17

Using scanning probe microscopy and temperature programed desorption we examined the interaction between water and two common clathrate-forming gases, methane and isobutane, at low temperature and low pressure. Water co-deposited with up to 10 –1 mbar methane or 10 –5 mbar isobutane at 140 K onto a Pt(111) substrate yielded pure crystalline ice, i.e., the exposure to up to ~ 10 7 gas molecules for each deposited water molecule did not have any detectable effect on the growing films. Exposing metastable, less than 2 molecular layers thick, water films to 10 –5 mbar methane does not alter their morphology, suggestingmore » that the presence of the Pt(111) surface is not a strong driver for hydrate formation. This weak water–gas interaction at low pressures is supported by our thermal desorption measurements from amorphous solid water and crystalline ice where 1 ML of methane desorbs near ~ 43 K and isobutane desorbs near ~ 100 K. As a result, similar desorption temperatures were observed for desorption from amorphous solid water.« less

The study of 'microsurfaces' using thermal desorption spectroscopy

NASA Technical Reports Server (NTRS)

Thomas, M. E.; Poppa, H.; Pound, G. M.

1979-01-01

The use of a newly combined ultrahigh vacuum technique for studying continuous and particulate evaporated thin films using thermal desorption spectroscopy (TDS), transmission electron microscopy (TEM), and transmission electron diffraction (TED) is discussed. It is shown that (1) CO thermal desorption energies of epitaxially deposited (111) Ni and (111) Pd surfaces agree perfectly with previously published data on bulk (111) single crystal, (2) contamination and surface structural differences can be detected using TDS as a surface probe and TEM as a complementary technique, and (3) CO desorption signals from deposited metal coverages of one-thousandth of a monolayer should be detectable. These results indicate that the chemisorption properties of supported 'microsurfaces' of metals can now be investigated with very high sensitivity. The combined use of TDS and TEM-TED experimental methods is a very powerful technique for fundamental studies in basic thin film physics and in catalysis.

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.

Atmospheric Pressure-Thermal Desorption (AP-TD)/Electrospray Ionization-Mass Spectrometry for the Rapid Analysis of Bacillus Spores

USDA-ARS?s Scientific Manuscript database

A technique is described where an atmospheric pressure-thermal desorption (AP-TD) device and electrospray ionization (ESI)-mass spectrometry are coupled and used for the rapid analysis of Bacillus spores in complex matrices. The resulting AP-TD/ESI-MS technique combines the generation of volatile co...

SUPERFUND TREATABILITY CLEARINGHOUSE: TECHNOLOGY DEMONSTRATION OF A THERMAL DESORPTION/UV PHOTOLYSIS PROCESS FOR DECONTAMINATING SOILS CONTAINING HERBICIDE ORANGE

EPA Science Inventory

This treatability study report presents the results of laboratory and field tests on the effectiveness of a new decontamination process for soils containing 2,4-D/2,4,5-T and traces of dioxin. The process employs three operations, thermal desorption, condensation and absorp...

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

DOE PAGES

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

DEMONSTRATION BULLETIN: THE ECO LOGIC THERMAL DESORPTION UNIT - MIDDLEGROUND LANDFILL - BAY CITY, MI - ELI ECO LOGIC INTERNATIONAL, INC.

EPA Science Inventory

ECO Logic has developed a thermal desorption unit 0"DU) for the treatment of soils contaminated with hazardous organic contaminants. This TDU has been designed to be used in conjunction with Eco Logic's patented gas-phase chemical reduction reactor. The Eco Logic reactor is the s...

POLYCYCLIC AROMATIC HYDROCARBON (PAH) SIZE DISTRIBUTIONS IN AEROSOLS FROM APPLIANCES OF RESIDENTIAL WOOD COMBUSTION AS DETERMINED BY DIRECT THERMAL DESORPTION - GC/MS

EPA Science Inventory

The paper describesd a direct thermal desorption (TDS) approach to determine the PAH composition (MW = 202-302 amu) in size-segregated aerosols from residential wood combustion (RWC). Six combustion tests are performed with two highly available wood fuel varieties, Douglas-fir (P...

Comparison between Thermal Desorption Tubes and Stainless Steel Canisters Used for Measuring Volatile Organic Compounds in Petrochemical Factories

PubMed Central

Chang, Cheng-Ping; Lin, Tser-Cheng; Lin, Yu-Wen; Hua, Yi-Chun; Chu, Wei-Ming; Lin, Tzu-Yu; Lin, Yi-Wen; Wu, Jyun-De

2016-01-01

Objective: The purpose of this study was to compare thermal desorption tubes and stainless steel canisters for measuring volatile organic compounds (VOCs) emitted from petrochemical factories. Methods: Twelve petrochemical factories in the Mailiao Industrial Complex were recruited for conducting the measurements of VOCs. Thermal desorption tubes and 6-l specially prepared stainless steel canisters were used to simultaneously perform active sampling of environmental air samples. The sampling time of the environmental air samples was set up on 6h close to a full work shift of the workers. A total of 94 pairwise air samples were collected by using the thermal adsorption tubes and stainless steel canisters in these 12 factories in the petrochemical industrial complex. To maximize the number of comparative data points, all the measurements from all the factories in different sampling times were lumped together to perform a linear regression analysis for each selected VOC. Pearson product–moment correlation coefficient was used to examine the correlation between the pairwise measurements of these two sampling methods. A paired t-test was also performed to examine whether the difference in the concentrations of each selected VOC measured by the two methods was statistically significant. Results: The correlation coefficients of seven compounds, including acetone, n-hexane, benzene, toluene, 1,2-dichloroethane, 1,3-butadiene, and styrene were >0.80 indicating the two sampling methods for these VOCs’ measurements had high consistency. The paired t-tests for the measurements of n-hexane, benzene, m/p-xylene, o-xylene, 1,2-dichloroethane, and 1,3-butadiene showed statistically significant difference (P-value < 0.05). This indicated that the two sampling methods had various degrees of systematic errors. Looking at the results of six chemicals and these systematic errors probably resulted from the differences of the detection limits in the two sampling methods for these VOCs. Conclusions: The comparison between the concentrations of each of the 10 selected VOCs measured by the two sampling methods indicted that the thermal desorption tubes provided high accuracy and precision measurements for acetone, benzene, and 1,3-butadiene. The accuracy and precision of using the thermal desorption tubes for measuring the VOCs can be improved due to new developments in sorbent materials, multi-sorbent designs, and thermal desorption instrumentation. More applications of thermal desorption tubes for measuring occupational and environmental hazardous agents can be anticipated. PMID:26585828

Comparison between Thermal Desorption Tubes and Stainless Steel Canisters Used for Measuring Volatile Organic Compounds in Petrochemical Factories.

PubMed

Chang, Cheng-Ping; Lin, Tser-Cheng; Lin, Yu-Wen; Hua, Yi-Chun; Chu, Wei-Ming; Lin, Tzu-Yu; Lin, Yi-Wen; Wu, Jyun-De

2016-04-01

The purpose of this study was to compare thermal desorption tubes and stainless steel canisters for measuring volatile organic compounds (VOCs) emitted from petrochemical factories. Twelve petrochemical factories in the Mailiao Industrial Complex were recruited for conducting the measurements of VOCs. Thermal desorption tubes and 6-l specially prepared stainless steel canisters were used to simultaneously perform active sampling of environmental air samples. The sampling time of the environmental air samples was set up on 6 h close to a full work shift of the workers. A total of 94 pairwise air samples were collected by using the thermal adsorption tubes and stainless steel canisters in these 12 factories in the petrochemical industrial complex. To maximize the number of comparative data points, all the measurements from all the factories in different sampling times were lumped together to perform a linear regression analysis for each selected VOC. Pearson product-moment correlation coefficient was used to examine the correlation between the pairwise measurements of these two sampling methods. A paired t-test was also performed to examine whether the difference in the concentrations of each selected VOC measured by the two methods was statistically significant. The correlation coefficients of seven compounds, including acetone, n-hexane, benzene, toluene, 1,2-dichloroethane, 1,3-butadiene, and styrene were >0.80 indicating the two sampling methods for these VOCs' measurements had high consistency. The paired t-tests for the measurements of n-hexane, benzene, m/p-xylene, o-xylene, 1,2-dichloroethane, and 1,3-butadiene showed statistically significant difference (P-value < 0.05). This indicated that the two sampling methods had various degrees of systematic errors. Looking at the results of six chemicals and these systematic errors probably resulted from the differences of the detection limits in the two sampling methods for these VOCs. The comparison between the concentrations of each of the 10 selected VOCs measured by the two sampling methods indicted that the thermal desorption tubes provided high accuracy and precision measurements for acetone, benzene, and 1,3-butadiene. The accuracy and precision of using the thermal desorption tubes for measuring the VOCs can be improved due to new developments in sorbent materials, multi-sorbent designs, and thermal desorption instrumentation. More applications of thermal desorption tubes for measuring occupational and environmental hazardous agents can be anticipated. © The Author 2015. Published by Oxford University Press on behalf of the British Occupational Hygiene Society.

A Technique for Thermal Desorption Analyses Suitable for Thermally-Labile, Volatile Compounds.

PubMed

Alborn, Hans T

2018-02-01

Many plant and insect interactions are governed by odors released by the plants or insects and there exists a continual need for new or improved methods to collect and identify these odors. Our group has for some time studied below-ground, plant-produced volatile signals affecting nematode and insect behavior. The research requires repeated sampling of volatiles of intact plant/soil systems in the laboratory as well as the field with the help of probes to minimize unwanted effects on the systems we are studying. After evaluating solid adsorbent filters with solvent extraction or solid phase micro extraction fiber sample collection, we found dynamic sampling of small air volumes on Tenax TA filters followed by thermal desorption sample introduction to be the most suitable analytical technique for our applications. Here we present the development and evaluation of a low-cost and relatively simple thermal desorption technique where a cold trap cooled with liquid carbon dioxide is added as an integral part of a splitless injector. Temperature gradient-based focusing and low thermal mass minimizes aerosol formation and eliminates the need for flash heating, resulting in low sample degradation comparable to solvent-based on-column injections. Additionally, since the presence of the cold trap does not affect normal splitless injections, on-the-fly switching between splitless and thermal desorption modes can be used for external standard quantification.

Injection of dust into the Martian atmosphere - Evidence from the Viking Gas Exchange experiment

NASA Technical Reports Server (NTRS)

Huguenin, R. L.; Harris, S. L.; Carter, R.

1986-01-01

The hypothesis that predawn midlatitude storms are triggered by a soil humidification process is examined. A freeze/thaw model of the process is evaluated in the Viking Gas Exchange experiments conducted on Mars. The humidification-driven desorption and desiccation state of Martian soil samples are analyzed. The periodic humidification of equatorial regolith soil is studied in terms of pore space pressure during desorption events and soil diffusivity; the thermal properties of the regolith surface layer are modeled using the program of Clifford (1984). Consideration is given to the diurnal and seasonal cycles of the humidification process, the permanent, low-albedo features in the midlatitudes, and the production of H2SO4 and HCl aerosols.

Effect of metal surfaces on matrix-assisted laser desorption/ionization analyte peak intensities.

PubMed

Kancharla, Vidhyullatha; Bashir, Sajid; Liu, Jingbo L; Ramirez, Oscar M; Derrick, Peter J; Beran, Kyle A

2017-10-01

Different metal surfaces in the form of transmission electron microscope grids were examined as support surfaces in matrix-assisted laser desorption/ionization time-of-flight mass spectrometry with a view towards enhancement of peptide signal intensity. The observed enhancement between 5-fold and 20-fold relative to the normal stainless steel slide was investigated by applying the thermal desorption model for matrix-assisted laser desorption/ionization. A simple model evaluates the impact that the thermal properties of the metals have on the ion yield of the analyte. It was observed that there was not a direct, or strong, correlation between the thermal properties of the metals and the corresponding ion yield of the peptides. The effects of both fixed and variable laser irradiances versus ion yield were also examined for the respective metals studied. In all cases the use of transmission electron microscope grids required much lower laser irradiances in order to generate similar peak intensities as those observed with a stainless steel surface.

Low-Energy Water Recovery from Subsurface Brines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choi, Young Chul; Kim, Gyu Dong; Hendren, Zachary

A novel non-aqueous phase solvent (NAS) desalination process was proposed and developed in this research project. The NAS desalination process uses less energy than thermal processes, doesn’t require any additional chemicals for precipitation, and can be utilized to treat high TDS brine. In this project, our experimental work determined that water solubility changes and selective absorption are the key characteristics of NAS technology for successful desalination. Three NAS desalination mechanisms were investigated: (1) CO2 switchable, (2) high-temp absorption to low-temp desorption (thermally switchable), and (3) low-temp absorption to high-temp desorption (thermally switchable). Among these mechanisms, thermally switchable (low-temp absorption tomore » high-temp desorption) showed the highest water recovery and relatively high salt rejection. A test procedure for semi-continuous, bench scale NAS desalination process was also developed and used to assess performance under a range of conditions.« less

Thermal and FTIR spectroscopic analysis of the interactions of aniline adsorbed on to MCM-41 mesoporous material.

PubMed

Eimer, Griselda A; Gómez Costa, Marcos B; Pierella, Liliana B; Anunziata, Oscar A

2003-07-15

The adsorption of aniline on Na-AlMCM-41 synthesized by us has been characterized by infrared spectroscopy, temperature programmed desorption (TPD), and differential thermal analysis methods. Aniline would be mostly bound to the mesostructure through weak pi interactions. On the mesostructure containing adsorbed water, the co-adsorption of aniline could occur by weak hydrogen bonding through surface water molecules. For water, two possible modes of adsorption have been identified. Different associations between aniline and hydrated and nonhydrated mesostructures have been evaluated in order to favor the posterior in situ polymerization of adsorbed aniline.

DOUBLE DCO{sup +} RINGS REVEAL CO ICE DESORPTION IN THE OUTER DISK AROUND IM LUP

DOE Office of Scientific and Technical Information (OSTI.GOV)

Öberg, Karin I.; Loomis, Ryan; Andrews, Sean M.

2015-09-10

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, C{sup 18}O 2–1, H{sup 13}CO{sup +} 3–2 and DCO{sup +} 3–2 emission at ∼0.″5 resolution. The images of these dust and gas tracers are clearly resolved. The DCO{sup +} line exhibits a striking pair of concentric rings of emission thatmore » peak at radii of ∼0.″6 and 2″ (∼90 and 300 AU, respectively). Based on disk chemistry model comparison, the inner DCO{sup +} ring is associated with the balance of CO freeze-out and thermal desorption due to a radial decrease in disk temperature. The outer DCO{sup +} 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 H{sub 2}D{sup +} to form the observed DCO{sup +} outer ring. These observations demonstrate that spatially resolved DCO{sup +} 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.« less

Development of a short path thermal desorption-gas chromatography/mass spectrometry method for the determination of polycyclic aromatic hydrocarbons in indoor air.

PubMed

Li, Yingjie; Xian, Qiming; Li, Li

2017-05-12

Polycyclic aromatic hydrocarbons (PAHs) are present in petroleum based products and are combustion by-products of organic matters. Determination of levels of PAHs in the indoor environment is important for assessing human exposure to these chemicals. A new short path thermal desorption (SPTD) gas chromatography/mass spectrometry (GC/MS) method for determining levels of PAHs in indoor air was developed. Thermal desorption (TD) tubes packed with glass beads, Carbopack C, and Carbopack B in sequence, were used for sample collection. Indoor air was sampled using a small portable pump over 7 days at 100ml/min. Target PAHs were thermally released and introduced into the GC/MS for analysis through the SPTD unit. During tube desorption, PAHs were cold trapped (-20°C) at the front end of the GC column. Thermal desorption efficiencies were 100% for PAHs with 2 and 3 rings, and 99-97% for PAHs with 4-6 rings. Relative standard deviation (RSD) values among replicate samples spiked at three different levels were around 10-20%. The detection limit of this method was at or below 0.1μg/m 3 except for naphthalene (0.61μg/m 3 ), fluorene (0.28μg/m 3 ) and phenanthrene (0.35μg/m 3 ). This method was applied to measure PAHs in indoor air in nine residential homes. The levels of PAHs in indoor air found in these nine homes are similar to indoor air values reported by others. Copyright © 2017 Elsevier B.V. All rights reserved.

Organic and inorganic decomposition products from the thermal desorption of atmospheric particles

NASA Astrophysics Data System (ADS)

Williams, B. J.; Zhang, Y.; Zuo, X.; Martinez, R. E.; Walker, M. J.; Kreisberg, N. M.; Goldstein, A. H.; Docherty, K. S.; Jimenez, J. L.

2015-12-01

Atmospheric aerosol composition is often analyzed using thermal desorption techniques to evaporate samples and deliver organic or inorganic molecules to various designs of detectors for identification and quantification. The organic aerosol (OA) fraction is composed of thousands of individual compounds, some with nitrogen- and sulfur-containing functionality, and often contains oligomeric material, much of which may be susceptible to decomposition upon heating. Here we analyze thermal decomposition products as measured by a thermal desorption aerosol gas chromatograph (TAG) capable of separating thermal decomposition products from thermally stable molecules. The TAG impacts particles onto a collection and thermal desorption (CTD) cell, and upon completion of sample collection, heats and transfers the sample in a helium flow up to 310 °C. Desorbed molecules are refocused at the head of a GC column that is held at 45 °C and any volatile decomposition products pass directly through the column and into an electron impact quadrupole mass spectrometer (MS). Analysis of the sample introduction (thermal decomposition) period reveals contributions of NO+ (m/z 30), NO2+ (m/z 46), SO+ (m/z 48), and SO2+ (m/z 64), derived from either inorganic or organic particle-phase nitrate and sulfate. CO2+ (m/z 44) makes up a major component of the decomposition signal, along with smaller contributions from other organic components that vary with the type of aerosol contributing to the signal (e.g., m/z 53, 82 observed here for isoprene-derived secondary OA). All of these ions are important for ambient aerosol analyzed with the aerosol mass spectrometer (AMS), suggesting similarity of the thermal desorption processes in both instruments. Ambient observations of these decomposition products compared to organic, nitrate, and sulfate mass concentrations measured by an AMS reveal good correlation, with improved correlations for OA when compared to the AMS oxygenated OA (OOA) component. TAG signal found in the traditional compound elution time period reveals higher correlations with AMS hydrocarbon-like OA (HOA) combined with the fraction of OOA that is less oxygenated. Potential to quantify nitrate and sulfate aerosol mass concentrations using the TAG system is explored through analysis of ammonium sulfate and ammonium nitrate standards. While chemical standards display a linear response in the TAG system, re-desorptions of the CTD cell following ambient sample analysis shows some signal carryover on sulfate and organics, and new desorption methods should be developed to improve throughput. Future standards should be composed of complex organic/inorganic mixtures, similar to what is found in the atmosphere, and perhaps will more accurately account for any aerosol mixture effects on compositional quantification.

Determination of off-flavor compounds, 2-methylisoborneol and geosmin, in salmon fillets using stir bar sorptive extraction–thermal desorption coupled with gas chromatography–mass spectrometry

USDA-ARS?s Scientific Manuscript database

A sensitive and solvent-less method for the determination of musty and earthy off-flavor compounds, 2-methylisoborneol (MIB) and geosmin (GSM), in salmon tissue was developed using stir bar sorptive extraction -thermal desorption coupled with gas chromatography -mass spectrometry (SBSE -TD -GCMS). M...

A kinetic Monte Carlo approach to diffusion-controlled thermal desorption spectroscopy

NASA Astrophysics Data System (ADS)

Schablitzki, T.; Rogal, J.; Drautz, R.

2017-06-01

Atomistic simulations of thermal desorption spectra for effusion from bulk materials to characterize binding or trapping sites are a challenging task as large system sizes as well as extended time scales are required. Here, we introduce an approach where we combine kinetic Monte Carlo with an analytic approximation of the superbasins within the framework of absorbing Markov chains. We apply our approach to the effusion of hydrogen from BCC iron, where the diffusion within bulk grains is coarse grained using absorbing Markov chains, which provide an exact solution of the dynamics within a superbasin. Our analytic approximation to the superbasin is transferable with respect to grain size and elliptical shapes and can be applied in simulations with constant temperature as well as constant heating rate. The resulting thermal desorption spectra are in close agreement with direct kinetic Monte Carlo simulations, but the calculations are computationally much more efficient. Our approach is thus applicable to much larger system sizes and provides a first step towards an atomistic understanding of the influence of structural features on the position and shape of peaks in thermal desorption spectra. This article is part of the themed issue 'The challenges of hydrogen and metals'.

An infrared measurement of chemical desorption from interstellar ice analogues

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Growth kinetics of indium metal atoms on Si(1 1 2) surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Raj, Vidur; Chauhan, Amit Kumar Singh; Gupta, Govind, E-mail: govind@nplindia.org

Graphical abstract: Controlled growth of indium atoms on Si(1 1 2) surface has been carried out systematically and the influence of substrate temperature on the kinetics is analysed under various growth conditions. Temperature induced anomalous layer-to-clusters transformation during thermal desorption has also been reported. - Highlights: • Controlled growth of indium atoms on Si(1 1 2) surface & their thermal stability. • Influence of substrate temperature on the kinetics under various growth conditions. • Temperature induced layer-to-clusters transformation during thermal desorption. - Abstract: The growth kinetics and desorption behavior of indium (In) atoms grown on high index Si(1 1 2)more » surface at different substrate temperatures has been studied. Auger electron spectroscopy analysis revealed that In growth at room temperature (RT) and high substrate temperature (HT) ∼250 °C follows Frank–van der Merve growth mode whereas at temperatures ≥450 °C, In growth evolves through Volmer–Weber growth mode. Thermal desorption studies of RT and 250 °C grown In/Si(1 1 2) systems show temperature induced rearrangement of In atoms over Si(1 1 2) surface leading to clusters to layer transformation. The monolayer and bilayer desorption energies for RT grown In/Si(1 1 2) system are calculated to be 2.5 eV and 1.52 eV, while for HT-250 °C the values are found to be 1.6 eV and 1.3 eV, respectively. This study demonstrates the effect of temperature on growth kinetics as well as on the multilayer/monolayer desorption pathway of In on Si(1 1 2) surface.« less

THERMAL DESORPTION MASS SPECTROMETRIC ANALYSIS OF ORGANIC AEROSOL FORMED FROM REACTIONS OF 1-TETRADECENE AND O3 IN THE PRESENCE OF ALCOHOLS AND CARBOXYLIC ACIDS. (R826235)

EPA Science Inventory

The chemistry of secondary organic aerosol formation from reactions of
1-tetradecene and O₃ in dry air in the presence of excess alcohols
and carboxylic acids was investigated in an environmental chamber using a
thermal desorption particle beam mass spec...

DART-MS analysis of inorganic explosives using high temperature thermal desorption†‡

PubMed Central

Sisco, Edward; Staymates, Matthew; Gillen, Greg

2018-01-01

An ambient mass spectrometry (MS) platform coupling resistive Joule heating thermal desorption (JHTD) and direct analysis in real time (DART) was implemented for the analysis of inorganic nitrite, nitrate, chlorate, and perchlorate salts. The resistive heating component generated discrete and rapid heating ramps and elevated temperatures, up to approximately 400 °C s−1 and 750 °C, by passing a few amperes of DC current through a nichrome wire. JHTD enhanced the utility and capabilities of traditional DART-MS for the trace detection of previously difficult to detect inorganic compounds. A partial factorial design of experiments (DOE) was implemented for the systematic evaluation of five system parameters. A base set of conditions for JHTD-DART-MS was derived from this evaluation, demonstrating sensitive detection of a range of inorganic oxidizer salts, down to single nanogram levels. DOE also identified JHTD filament current and in-source collision induced dissociation (CID) energy as inducing the greatest effect on system response. Tuning of JHTD current provided a method for controlling the relative degrees of thermal desorption and thermal decomposition. Furthermore, in-source CID provided manipulation of adduct and cluster fragmentation, optimizing the detection of molecular anion species. Finally, the differential thermal desorption nature of the JHTD-DART platform demonstrated efficient desorption and detection of organic and inorganic explosive mixtures, with each desorbing at its respective optimal temperature. PMID:29651308

Dynamic Monte Carlo description of thermal desorption processes

NASA Astrophysics Data System (ADS)

Weinketz, Sieghard

1994-07-01

The applicability of the dynamic Monte Carlo method of Fichthorn and Weinberg, in which the time evolution of a system is described in terms of the absolute number of different microscopic possible events and their associated transition rates, is discussed for the case of thermal desorption simulations. It is shown that the definition of the time increment at each successful event leads naturally to the macroscopic differential equation of desorption, in the case of simple first- and second-order processes in which the only possible events are desorption and diffusion. This equivalence is numerically demonstrated for a second-order case. In the sequence, the equivalence of this method with the Monte Carlo method of Sales and Zgrablich for more complex desorption processes, allowing for lateral interactions between adsorbates, is shown, even though the dynamic Monte Carlo method does not bear their limitation of a rapid surface diffusion condition, thus being able to describe a more complex ``kinetics'' of surface reactive processes, and therefore be applied to a wider class of phenomena, such as surface catalysis.

GC-MS determination of parabens, triclosan and methyl triclosan in water by in situ derivatisation and stir-bar sorptive extraction.

PubMed

Casas Ferreira, Ana María; Möder, Monika; Fernández Laespada, María Esther

2011-01-01

Stir-bar sorptive extraction in combination with an in situ derivatisation reaction and thermal desorption-gas chromatography-mass spectrometry was successfully applied to determine parabens (methylparaben, isopropylparaben, n-propylparaben, butylparaben and benzylparaben), triclosan and methyltriclosan in water samples. This approach improves both the extraction efficiency and the sensitivity in the GC in a simple way since the derivatisation reaction occurs at the same time as the extraction procedure. The in situ derivatisation reaction was carried out with acetic anhydride under alkaline conditions. Thermal desorption parameters (cryofocusing temperature, desorption flow, desorption time, desorption temperature) were optimised using a Box-Behnken experimental design. All the analytes gave recoveries higher than 79%, except methylparaben (22%). The method afforded detection limits between 0.64 and 4.12 ng/L, with good reproducibility and accuracy values. The feasibility of the method for the determination of analytes in water samples was checked in tap water and untreated and treated wastewater.

Measurement of toxic volatile organic compounds in indoor air of semiconductor foundries using multisorbent adsorption/thermal desorption coupled with gas chromatography-mass spectrometry.

PubMed

Wu, Chien-Hou; Lin, Ming-Nan; Feng, Chien-Tai; Yang, Kuang-Ling; Lo, Yu-Shiu; Lo, Jiunn-Guang

2003-05-09

A method for the qualitative and quantitative analysis of volatile organic compounds (VOCs) in the air of class-100 clean rooms at semiconductor fabrication facilities was developed. Air samples from two semiconductor factories were collected each hour on multisorbent tubes (including Carbopack B, Carbopack C, and Carbosieve SIII) with a 24-h automatic active sampling system and analyzed using adsorption/thermal desorption coupled with gas chromatography-mass spectrometry. Experimental parameters, including thermal desorption temperature, desorption time, and cryofocusing temperature, were optimized. The average recoveries and the method detection limits for the target compounds were in the range 94-101% and 0.31-0.89 ppb, respectively, under the conditions of a 1 L sampling volume and 80% relative humidity. VOCs such as acetone, isopropyl alcohol, 2-heptanone, and toluene, which are commonly used in the semiconductor and electronics industries, were detected and accurately quantified with the established method. Temporal variations of the analyte concentrations observed were attributed to the improper use of organic solvents during operation.

24-HOUR DIFFUSIVE SAMPLING OF 1,3-BUTADIENE IN AIR ONTO CARBOPACK X SOLID ADSORBENT FOLLOWED BY THERMAL DESORPTION/GC/MS ANALYSIS - FEASIBILITY STUDY

EPA Science Inventory

Diffusive sampling of 1,3-butadiene for 24 hr onto the graphitic adsorbent Carbopack X packed in a stainless steel tube badge (6.3 mm o.d., 5 mm i.d., and 90 mm in length) with analysis by thermal desorption/gas chromatography (GC)/mass spectrometry (MS) has been evaluated in con...

Analysis of airborne pesticides from different chemical classes adsorbed on Radiello® Tenax® passive tubes by thermal-desorption-GC/MS.

PubMed

Raeppel, Caroline; Fabritius, Marie; Nief, Marie; Appenzeller, Brice M R; Briand, Olivier; Tuduri, Ludovic; Millet, Maurice

2015-02-01

An analytical methodology using automatic thermal desorption (ATD) and GC/MS was developed for the determination of 28 pesticides of different chemical classes (dichlobenil, carbofuran, trifluralin, clopyralid, carbaryl, flazasulfuron, mecoprop-P, dicamba, 2,4-MCPA, dichlorprop, 2,4-D, triclopyr, cyprodinil, bromoxynil, fluroxypyr, oxadiazon, myclobutanil, buprofezin, picloram, trinexapac-p-ethyl, ioxynil, diflufenican, tebuconazole, bifenthrin, isoxaben, alphacypermethrin, fenoxaprop and tau-fluvalinate) commonly used in nonagricultural areas in atmospheric samples. This methodology was developed to evaluate the indoor and outdoor atmospheric contamination by nonagricultural pesticides. Pesticides were sampled passive sampling tubes containing Tenax® adsorbent. Since most of these pesticides are polar (clopyralid, mecoprop-P, dicamba, 2,4-MCPA, dichlorprop, 2,4-D, triclopyr, bromoxynil, fluroxypyr, picloram, trinexapac-p-ethyl and ioxynil), a derivatisation step is required. For this purpose, a silylation step using N-(t-butyldimethylsilyl)-N-methyltrifluoroacetamide (MtBSTFA) was added before thermal desorption. This agent was chosen since it delivers very specific ions on electronic impact (m/z = M-57). This method was established with special consideration for optimal thermal desorption conditions (desorption temperature, desorb flow and duration; trap heating duration and flow; outlet split), linear ranges, limits of quantification and detection which varied from 0.005 to 10 ng and from 0.001 to 2.5 ng, respectively, for an uncertainty varied from 8 to 30 %. The method was applied in situ to the analysis of passive tubes exposed during herbicide application to an industrial site in east of France.

Desorption in Mass Spectrometry.

PubMed

Usmanov, Dilshadbek Tursunbayevich; Ninomiya, Satoshi; Chen, Lee Chuin; Saha, Subhrakanti; Mandal, Mridul Kanti; Sakai, Yuji; Takaishi, Rio; Habib, Ahsan; Hiraoka, Kenzo; Yoshimura, Kentaro; Takeda, Sen; Wada, Hiroshi; Nonami, Hiroshi

2017-01-01

In mass spectrometry, analytes must be released in the gas phase. There are two representative methods for the gasification of the condensed samples, i.e. , ablation and desorption. While ablation is based on the explosion induced by the energy accumulated in the condensed matrix, desorption is a single molecular process taking place on the surface. In this paper, desorption methods for mass spectrometry developed in our laboratory: flash heating/rapid cooling, Leidenfrost phenomenon-assisted thermal desorption (LPTD), solid/solid friction, liquid/solid friction, electrospray droplet impact (EDI) ionization/desorption, and probe electrospray ionization (PESI), will be described. All the methods are concerned with the surface and interface phenomena. The concept of how to desorb less-volatility compounds from the surface will be discussed.

Thermal stability of single-side hydrogenated graphene

NASA Astrophysics Data System (ADS)

Openov, L. A.; Podlivaev, A. I.

2012-11-01

The temperature dependence of the time of hydrogen desorption from single-side hydrogenated graphene is calculated using molecular dynamics simulation. The activation energy ( E a = 0.75 ± 0.10 eV) and the frequency factor ( A = (2.5 ± 1.0) × 1015 s-1) of the desorption are found. This quasi-two-dimensional carbon-hydrogen system is shown to have a relatively low thermal stability, which makes it difficult to use it in practice.

Mercury recovery using a fluidized bed

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harriss, C.; Baum, D.L. Jr.

1996-12-31

Philip Environmental Services Corporation`s (Philip`s) innovative fluidized bed thermal desorption system recovers mercury from contaminated soil. Referred to as the Thermal Recycling System, Philip has constructed a mobile thermal desorption system that has a processing rate up to five tons per hour. The system includes a continuous-feed system, all radiant heat, inert gas atmosphere, hot gas filter, two-stage cooling, and a water treatment system. Based on treatability studies, the processed soil can meet cleanup objectives as low as two milligrams per kilogram and passes the mercury toxicity characteristic leaching procedure test. 4 refs., 2 figs., 1 tab.

Organic and inorganic decomposition products from the thermal desorption of atmospheric particles

NASA Astrophysics Data System (ADS)

Williams, Brent J.; Zhang, Yaping; Zuo, Xiaochen; Martinez, Raul E.; Walker, Michael J.; Kreisberg, Nathan M.; Goldstein, Allen H.; Docherty, Kenneth S.; Jimenez, Jose L.

2016-04-01

Atmospheric aerosol composition is often analyzed using thermal desorption techniques to evaporate samples and deliver organic or inorganic molecules to various designs of detectors for identification and quantification. The organic aerosol (OA) fraction is composed of thousands of individual compounds, some with nitrogen- and sulfur-containing functionality and, often contains oligomeric material, much of which may be susceptible to decomposition upon heating. Here we analyze thermal decomposition products as measured by a thermal desorption aerosol gas chromatograph (TAG) capable of separating thermal decomposition products from thermally stable molecules. The TAG impacts particles onto a collection and thermal desorption (CTD) cell, and upon completion of sample collection, heats and transfers the sample in a helium flow up to 310 °C. Desorbed molecules are refocused at the head of a gas chromatography column that is held at 45 °C and any volatile decomposition products pass directly through the column and into an electron impact quadrupole mass spectrometer. Analysis of the sample introduction (thermal decomposition) period reveals contributions of NO+ (m/z 30), NO2+ (m/z 46), SO+ (m/z 48), and SO2+ (m/z 64), derived from either inorganic or organic particle-phase nitrate and sulfate. CO2+ (m/z 44) makes up a major component of the decomposition signal, along with smaller contributions from other organic components that vary with the type of aerosol contributing to the signal (e.g., m/z 53, 82 observed here for isoprene-derived secondary OA). All of these ions are important for ambient aerosol analyzed with the aerosol mass spectrometer (AMS), suggesting similarity of the thermal desorption processes in both instruments. Ambient observations of these decomposition products compared to organic, nitrate, and sulfate mass concentrations measured by an AMS reveal good correlation, with improved correlations for OA when compared to the AMS oxygenated OA (OOA) component. TAG signal found in the traditional compound elution time period reveals higher correlations with AMS hydrocarbon-like OA (HOA) combined with the fraction of OOA that is less oxygenated. Potential to quantify nitrate and sulfate aerosol mass concentrations using the TAG system is explored through analysis of ammonium sulfate and ammonium nitrate standards. While chemical standards display a linear response in the TAG system, redesorptions of the CTD cell following ambient sample analysis show some signal carryover on sulfate and organics, and new desorption methods should be developed to improve throughput. Future standards should be composed of complex organic/inorganic mixtures, similar to what is found in the atmosphere, and perhaps will more accurately account for any aerosol mixture effects on compositional quantification.

Organic and inorganic decomposition products from the thermal desorption of atmospheric particles

DOE PAGES

Williams, Brent J.; Zhang, Yaping; Zuo, Xiaochen; ...

2016-04-11

Here, atmospheric aerosol composition is often analyzed using thermal desorption techniques to evaporate samples and deliver organic or inorganic molecules to various designs of detectors for identification and quantification. The organic aerosol (OA) fraction is composed of thousands of individual compounds, some with nitrogen- and sulfur-containing functionality and, often contains oligomeric material, much of which may be susceptible to decomposition upon heating. Here we analyze thermal decomposition products as measured by a thermal desorption aerosol gas chromatograph (TAG) capable of separating thermal decomposition products from thermally stable molecules. The TAG impacts particles onto a collection and thermal desorption (CTD) cell, and upon completionmore » of sample collection, heats and transfers the sample in a helium flow up to 310 °C. Desorbed molecules are refocused at the head of a gas chromatography column that is held at 45 °C and any volatile decomposition products pass directly through the column and into an electron impact quadrupole mass spectrometer. Analysis of the sample introduction (thermal decomposition) period reveals contributions of NO + ( m/z 30), NO 2 + ( m/z 46), SO + ( m/z 48), and SO 2 + ( m/z 64), derived from either inorganic or organic particle-phase nitrate and sulfate. CO 2 + ( m/z 44) makes up a major component of the decomposition signal, along with smaller contributions from other organic components that vary with the type of aerosol contributing to the signal (e.g., m/z 53, 82 observed here for isoprene-derived secondary OA). All of these ions are important for ambient aerosol analyzed with the aerosol mass spectrometer (AMS), suggesting similarity of the thermal desorption processes in both instruments. Ambient observations of these decomposition products compared to organic, nitrate, and sulfate mass concentrations measured by an AMS reveal good correlation, with improved correlations for OA when compared to the AMS oxygenated OA (OOA) component. TAG signal found in the traditional compound elution time period reveals higher correlations with AMS hydrocarbon-like OA (HOA) combined with the fraction of OOA that is less oxygenated. Potential to quantify nitrate and sulfate aerosol mass concentrations using the TAG system is explored through analysis of ammonium sulfate and ammonium nitrate standards. While chemical standards display a linear response in the TAG system, redesorptions of the CTD cell following ambient sample analysis show some signal carryover on sulfate and organics, and new desorption methods should be developed to improve throughput. Future standards should be composed of complex organic/inorganic mixtures, similar to what is found in the atmosphere, and perhaps will more accurately account for any aerosol mixture effects on compositional quantification.« less

Gas storage carbon with enhanced thermal conductivity

DOEpatents

Burchell, Timothy D.; Rogers, Michael Ray; Judkins, Roddie R.

2000-01-01

A carbon fiber carbon matrix hybrid adsorbent monolith with enhanced thermal conductivity for storing and releasing gas through adsorption and desorption is disclosed. The heat of adsorption of the gas species being adsorbed is sufficiently large to cause hybrid monolith heating during adsorption and hybrid monolith cooling during desorption which significantly reduces the storage capacity of the hybrid monolith, or efficiency and economics of a gas separation process. The extent of this phenomenon depends, to a large extent, on the thermal conductivity of the adsorbent hybrid monolith. This invention is a hybrid version of a carbon fiber monolith, which offers significant enhancements to thermal conductivity and potential for improved gas separation and storage systems.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zubkov, Tykhon; Smith, R. Scott; Engstrom, Todd R.

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 Kmore » 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.« less

Agile Thermal Management STT-RX. Catalytic Influence of Ni-based Additives on the Dehydrogentation Properties of Ball Milled MgH2 (PREPRINT)

DTIC Science & Technology

2011-12-01

Wronski: Particle size, grain size and gamma-MgH2 effects on the desorption properties of nanocrystal- line commercial magnesium hydride processed...Catalytic effects of various forms of nickel on the synthesis rate and hydrogen desorption properties of nanocrystalline magnesium hydride (MgH2...dehydrogenation reaction. 15. SUBJECT TERMS magnesium hydride , MgH, thermal energy storage materials, endothermic reaction 16. SECURITY CLASSIFICATION

Thermodynamics and performance of the Mg-H-F system for thermochemical energy storage applications.

PubMed

Tortoza, Mariana S; Humphries, Terry D; Sheppard, Drew A; Paskevicius, Mark; Rowles, Matthew R; Sofianos, M Veronica; Aguey-Zinsou, Kondo-Francois; Buckley, Craig E

2018-01-24

Magnesium hydride (MgH 2 ) is a hydrogen storage material that operates at temperatures above 300 °C. Unfortunately, magnesium sintering occurs above 420 °C, inhibiting its application as a thermal energy storage material. In this study, the substitution of fluorine for hydrogen in MgH 2 to form a range of Mg(H x F 1-x ) 2 (x = 1, 0.95, 0.85, 0.70, 0.50, 0) composites has been utilised to thermodynamically stabilise the material, so it can be used as a thermochemical energy storage material that can replace molten salts in concentrating solar thermal plants. These materials have been studied by in situ synchrotron X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis, temperature-programmed-desorption mass spectrometry and Pressure-Composition-Isothermal (PCI) analysis. Thermal analysis has determined that the thermal stability of Mg-H-F solid solutions increases proportionally with fluorine content, with Mg(H 0.85 F 0.15 ) 2 having a maximum rate of H 2 desorption at 434 °C, with a practical hydrogen capacity of 4.6 ± 0.2 wt% H 2 (theoretical 5.4 wt% H 2 ). An extremely stable Mg(H 0.43 F 0.57 ) 2 phase is formed upon the decomposition of each Mg-H-F composition of which the remaining H 2 is not released until above 505 °C. PCI measurements of Mg(H 0.85 F 0.15 ) 2 have determined the enthalpy (ΔH des ) to be 73.6 ± 0.2 kJ mol -1 H 2 and entropy (ΔS des ) to be 131.2 ± 0.2 J K -1 mol -1 H 2 , which is slightly lower than MgH 2 with ΔH des of 74.06 kJ mol -1 H 2 and ΔS des = 133.4 J K -1 mol -1 H 2 . Cycling studies of Mg(H 0.85 F 0.15 ) 2 over six absorption/desorption cycles between 425 and 480 °C show an increased usable cycling temperature of ∼80 °C compared to bulk MgH 2 , increasing the thermal operating temperatures for technological applications.

Combined Atomic Force Microscope-Based Topographical Imaging and Nanometer Scale Resolved Proximal Probe Thermal Desorption/Electrospray Ionization-Mass Spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ovchinnikova, Olga S; Nikiforov, Maxim; Bradshaw, James A

2011-01-01

Nanometer scale proximal probe thermal desorption/electrospray ionization mass spectrometry (TD/ESI-MS) was demonstrated for molecular surface sampling of caffeine from a thin film using a 30 nm diameter nano-thermal analysis (nano-TA) probe tip in an atomic force microscope (AFM) coupled via a vapor transfer line and ESI interface to a MS detection platform. Using a probe temperature of 350 C and a spot sampling time of 30 s, conical desorption craters 250 nm in diameter and 100 nm deep were created as shown through subsequent topographical imaging of the surface within the same system. Automated sampling of a 5 x 2more » array of spots, with 2 m spacing between spots, and real time selective detection of the desorbed caffeine using tandem mass spectrometry was also demonstrated. Estimated from the crater volume (~2x106 nm3), only about 10 amol (2 fg) of caffeine was liberated from each thermal desorption crater in the thin film. These results illustrate a relatively simple experimental setup and means to acquire in automated fashion sub-micrometer scale spatial sampling resolution and mass spectral detection of materials amenable to TD. The ability to achieve MS-based chemical imaging with 250 nm scale spatial resolution with this system is anticipated.« less

Determination of phenolic priority pollutants utilizing permeation sampling method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Guozheng.

1990-01-01

A passive permeation sampling method for the determination of phenolic priority pollutants in water was developed. Phenols in an aqueous solution permeate a polymeric membrane and are collected on a solid adsorbent in a sampling device. Both solvent and thermal desorption techniques were employed to recovery phenolic pollutants collected. In the solvent desorption, phenolic compounds collected on the XAD-7 resin, and then desorbed by acetonitrile. In the thermal desorption, phenolic compounds collected on Tenax-TA were recovered thermally, Separation and quantification is achieved by a SPB-5 capillary column gas chromatography using a flame ionization detector. There are linear relationships between themore » amount of phenolic compounds collected and the products of the exposure times and concentrations over the range from 5 ppb to 20 ppm with precisions no worse than 13%. The permeation rates of the phenolic pollutants depend upon the exposure temperature, solution pH and membrane area. Samples collected can be stored for up to two weeks without loss. This method provides a simple, convenient and inexpensive way for monitoring the time-weighted-average concentration without the use of a pumping system. An automated sampler which combines the permeation and the thermal desorption techniques together was also developed for water sample obtained from grab sampling. The on-line setup provides a high degree of automation. Detection limits at 10 ppb can be achieved using this sampler.« less

Desorption in Mass Spectrometry

PubMed Central

Usmanov, Dilshadbek Tursunbayevich; Ninomiya, Satoshi; Chen, Lee Chuin; Saha, Subhrakanti; Mandal, Mridul Kanti; Sakai, Yuji; Takaishi, Rio; Habib, Ahsan; Hiraoka, Kenzo; Yoshimura, Kentaro; Takeda, Sen; Wada, Hiroshi; Nonami, Hiroshi

2017-01-01

In mass spectrometry, analytes must be released in the gas phase. There are two representative methods for the gasification of the condensed samples, i.e., ablation and desorption. While ablation is based on the explosion induced by the energy accumulated in the condensed matrix, desorption is a single molecular process taking place on the surface. In this paper, desorption methods for mass spectrometry developed in our laboratory: flash heating/rapid cooling, Leidenfrost phenomenon-assisted thermal desorption (LPTD), solid/solid friction, liquid/solid friction, electrospray droplet impact (EDI) ionization/desorption, and probe electrospray ionization (PESI), will be described. All the methods are concerned with the surface and interface phenomena. The concept of how to desorb less-volatility compounds from the surface will be discussed. PMID:28337398

Thermal desorption of metals from tungsten single crystal surfaces

NASA Technical Reports Server (NTRS)

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

1975-01-01

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

Thermal desorption spectroscopy of high fluence irradiated ultrafine and nanocrystalline tungsten: helium trapping and desorption correlated with morphology

NASA Astrophysics Data System (ADS)

El-Atwani, O.; Taylor, C. N.; Frishkoff, J.; Harlow, W.; Esquivel, E.; Maloy, S. A.; Taheri, M. L.

2018-01-01

Microstructural changes due to displacement damage and helium desorption are two phenomena that occur in tungsten plasma facing materials in fusion reactors. Nanocrystalline metals are being investigated as radiation tolerant materials that can mitigate these microstructural changes and better trap helium along their grain boundaries. Here, we investigate the performance of three tungsten grades (nanocrystalline, ultrafine and ITER grade tungsten), exposed to a high fluence of 4 keV helium at both RT and 773 K, during a thermal desorption spectroscopy (TDS) experiment. An investigation of the microstructure in pre-and post-TDS sample sets was performed. The amount of desorbed helium was shown to be highest in the ITER grade tungsten and lowest in the nanocrystalline tungsten. Correlating the desorption spectra and the microstructure (grain boundaries decorated with nanopores and crack formation) and comparing with previous literature on coarse grained tungsten samples at similar irradiation and TDS conditions, revealed the importance of grain boundaries in trapping helium and limiting helium desorption up to a high temperature of 1350 K in agreement with transmission electron microscopy studies on helium irradiated tungsten which showed preferential and large facetted bubble formation along the grain boundaries in the nanocrystalline tungsten grade.

Thermal desorption spectroscopy of high fluence irradiated ultrafine and nanocrystalline tungsten: helium trapping and desorption correlated with morphology

DOE PAGES

El-Atwani, Osman; Taylor, Chase N.; Frishkoff, James; ...

2017-11-09

Here, microstructural changes due to displacement damage and helium desorption are two phenomena that occur in tungsten plasma facing materials in fusion reactors. Nanocrystalline metals are being investigated as radiation tolerant materials that can mitigate these microstructural changes and better trap helium along their grain boundaries. Here, we investigate the performance of three tungsten grades (nanocrystalline, ultrafine and ITER grade tungsten), exposed to a high fluence of 4 keV helium at both RT and 773 K, during a thermal desorption spectroscopy (TDS) experiment. An investigation of the microstructure in pre-and post-TDS sample sets was performed. The amount of desorbed heliummore » was shown to be highest in the ITER grade tungsten and lowest in the nanocrystalline tungsten. Correlating the desorption spectra and the microstructure (grain boundaries decorated with nanopores and crack formation) and comparing with previous literature on coarse grained tungsten samples at similar irradiation and TDS conditions, revealed the importance of grain boundaries in trapping helium and limiting helium desorption up to a high temperature of 1350 K in agreement with transmission electron microscopy studies on helium irradiated tungsten which showed preferential and large facetted bubble formation along the grain boundaries in the nanocrystalline tungsten grade.« less

Lateral Interactions in Monolayer Thick Mercury Films

NASA Astrophysics Data System (ADS)

Kime, Yolanda Jan

An understanding of lateral adatom-adatom interactions is often an important part of understanding electronic structure and adsorption energetics in monolayer thick films. In this dissertation I use angle-resolved photoemission and thermal desorption spectroscopies to explore the relationship between the adatom-adatom interaction and other characteristics of the adlayer, such as electronic structure, defects, or coexistent structural phases in the adlayer. Since Hg binds weakly to many substrates, the lateral interactions are often a major contribution to the dynamics of the overlayer. Hg adlayer systems are thus ideal for probing lateral interactions. The electronic structures of Hg adlayers on Ag(100), Cu(100), and Cu_3Au(100) are studied with angle-resolved ultraviolet photoemission. The Hg atomic 5d_{5/2} electronic band is observed to split into two levels following adsorption onto some surfaces. The energetic splitting of the Hg 5d_{5/2} level is found to be directly correlated to the adlayer homogeneous strain energy. The existence of the split off level also depends on the order or disorder of the Hg adlayer. The energetics of Hg adsorption on Cu(100) are probed using thermal desorption spectroscopy. Two different ordered adlayer structures are observed for Hg adsorption on Cu(100) at 200 K. Under some adsorption conditions and over a range of exposures, the two phases are seen to coexist on the surface prior to the thermal desorption process. A phase transition from the more dense to the less dense phase is observed to occur during the thermal desorption process. Inherent differences in defect densities are responsible for the observed differences between lateral interactions measured previously with equilibrium (atom beam scattering) and as measured by the non-equilibrium (thermal desorption) technique reported here. Theoretical and experimental evidence for an indirect through-metal interaction between adatoms is also discussed. Although through-metal interactions may play a role in some adsorption systems, there is little compelling evidence that this effect is significant in many experimental reports where the through metal bond is invoked.

The analysis of clingfilms by infrared spectroscopy and thermal desorption capillary gas chromatography.

PubMed

Gilburt, J; Ingram, J M; Scott, M P; Underhill, M

1991-01-01

An automated thermal desorption gas chromatography technique has been adapted to analyse traces of volatile compounds in proprietary food-wrapping films. Fourteen brands of polyvinylchloride film, seven brands of polyethylene film and one polyvinylidene chloride film were discriminated. Prior infrared analysis was used to identify the polymer type. The chromatograms showed minor changes in volatiles along the length of a roll of film and major changes in films exposed to daylight or in contact with cannabis resin.

Evaporation Rates of Chemical Warfare Agents Using 5-CM Wind Tunnels I. CASARM Sulfur Mustard (HD) from Glass

DTIC Science & Technology

2008-10-01

Blank CONTENTS 1. INTRODUCTION 9 2. EXPERIMENTAL PROCEDURES 9 2.1 Wind Tunnel 9 2.2 Agent 10 2.3 Gas Chromatography /Mass Spectrometry Detection 10...protective equipment. 2.3 Gas Chromatography /Mass Spectrometry Detection (GC/MSD) The GC/MSD analysis of the thermal desorption tubes was performed on a...coupled to thermal desorption tubes that were analyzed using gas chromatography /mass spectrometry detection (GC/MSD). Differences between the tunnels

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.

A green strategy for desorption of trihalomethanes adsorbed by humin and reuse of the fixed bed column.

PubMed

Cunha, G C; Romão, L P C; Santos, M C; Costa, A S; Alexandre, M R

2012-03-30

The objective of the present work was to develop a thermal desorption method for the removal of trihalomethanes (THM) adsorbed by humin, followed by multiple recycling of the fixed bed column in order to avoid excessive consumption of materials and reduce operating costs. The results obtained for adsorption on a fixed bed column confirmed the effectiveness of humin as an adsorbent, extracting between 45.9% and 90.1% of the total THM (TTHM). In none of the tests was the column fully saturated after 10h. Experiments involving thermal desorption were used to evaluate the potential of the technique for column regeneration. The adsorptive capacity of the humin bed increased significantly (p<0.05) between the first and fifth desorption cycle, by 18.9%, 18.1%, 24.2%, 20.2% and 24.2% for CHBr(3), CHBr(2)Cl, CHBrCl(2), CHCl(3) and TTHM, respectively. Copyright © 2011 Elsevier B.V. All rights reserved.

Analysis of volatiles in fire debris by combination of activated charcoal strips (ACS) and automated thermal desorption-gas chromatography-mass spectrometry (ATD/GC-MS).

PubMed

Martin Fabritius, Marie; Broillet, Alain; König, Stefan; Weinmann, Wolfgang

2018-06-04

Adsorption of volatiles in gaseous phase to activated charcoal strip (ACS) is one possibility for the extraction and concentration of ignitable liquid residues (ILRs) from fire debris in arson investigations. Besides liquid extraction using carbon dioxide or hexane, automated thermo-desorption can be used to transfer adsorbed residues to direct analysis by gas chromatography-mass spectrometry (GC-MS). We present a fire debris analysis work-flow with headspace adsorption of volatiles onto ACS and subsequent automated thermo-desorption (ATD) GC-MS analysis. Only a small portion of the ACS is inserted in the ATD tube for thermal desorption coupled to GC-MS, allowing for subsequent confirmation analysis with another portion of the same ACS. This approach is a promising alternative to the routinely used ACS method with solvent extraction of retained volatiles, and the application to fire debris analysis is demonstrated. Copyright © 2018 Elsevier B.V. All rights reserved.

IMPULSIVE SPOT HEATING AND THERMAL EXPLOSION OF INTERSTELLAR GRAINS REVISITED

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ivlev, A. V.; Röcker, T. B.; Vasyunin, A.

The problem of the impulsive heating of dust grains in cold, dense interstellar clouds is revisited theoretically with the aim of better understanding the leading mechanisms of the explosive desorption of icy mantles. We rigorously show that if the heating of a reactive medium occurs within a sufficiently localized spot (e.g., the heating of mantles by cosmic rays (CRs)), then the subsequent thermal evolution is characterized by a single dimensionless number λ. This number identifies a bifurcation between two distinct regimes: when λ exceeds a critical value (threshold), the heat equation exhibits the explosive solution, i.e., the thermal (chemical) explosionmore » is triggered. Otherwise, thermal diffusion causes the deposited heat to spread over the entire grain—this regime is commonly known as whole-grain heating. The theory allows us to find a critical combination of physical parameters that govern the explosion of icy mantles due to impulsive spot heating. In particular, our calculations suggest that heavy CR species (e.g., iron ions) colliding with dust are able to trigger the explosion. Based on recently calculated local CR spectra, we estimate the expected rate of explosive desorption. The efficiency of the desorption, which in principle affects all solid species independent of their binding energy, is shown to be comparable to other CR desorption mechanisms typically considered in the literature. Also, the theory allows us to estimate the maximum abundances of reactive species that may be stored in the mantles, which provides important constraints on the available astrochemical models.« less

Thermal enhancement cartridge heater modified (TECH Mod) tritium hydride bed development, Part 1 - Design and fabrication

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klein, J.E.; Estochen, E.G.

The Savannah River Site (SRS) tritium facilities have used first generation (Gen1) LaNi{sub 4.25}Al{sub 0.75} (LANA0.75) metal hydride storage beds for tritium absorption, storage, and desorption. The Gen1 design utilizes hot and cold nitrogen supplies to thermally cycle these beds. Second and third generation (Gen2 and Gen3) storage bed designs include heat conducting foam and divider plates to spatially fix the hydride within the bed. For thermal cycling, the Gen2 and Gen3 beds utilize internal electric heaters and glovebox atmosphere flow over the bed inside the bed external jacket for cooling. The currently installed Gen1 beds require replacement due tomore » tritium aging effects on the LANA0.75 material, and cannot be replaced with Gen2 or Gen3 beds due to different designs of these beds. At the end of service life, Gen1 bed desorption efficiencies are limited by the upper temperature of hot nitrogen supply. To increase end-of-life desorption efficiency, the Gen1 bed design was modified, and a Thermal Enhancement Cartridge Heater Modified (TECH Mod) bed was developed. Internal electric cartridge heaters in the new design to improve end-of-life desorption, and also permit in-bed tritium accountability (IBA) calibration measurements to be made without the use of process tritium. Additional enhancements implemented into the TECH Mod design are also discussed. (authors)« less

THERMAL ENHANCEMENT CARTRIDGE HEATER MODIFIED TECH MOD TRITIUM HYDRIDE BED DEVELOPMENT PART I DESIGN AND FABRICATION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klein, J.; Estochen, E.

The Savannah River Site (SRS) tritium facilities have used 1{sup st} generation (Gen1) LaNi{sub 4.25}Al{sub 0.75} (LANA0.75) metal hydride storage beds for tritium absorption, storage, and desorption. The Gen1 design utilizes hot and cold nitrogen supplies to thermally cycle these beds. Second and 3{sup rd} generation (Gen2 and Gen3) storage bed designs include heat conducting foam and divider plates to spatially fix the hydride within the bed. For thermal cycling, the Gen2 and Gen 3 beds utilize internal electric heaters and glovebox atmosphere flow over the bed inside the bed external jacket for cooling. The currently installed Gen1 beds requiremore » replacement due to tritium aging effects on the LANA0.75 material, and cannot be replaced with Gen2 or Gen3 beds due to different designs of these beds. At the end of service life, Gen1 bed desorption efficiencies are limited by the upper temperature of hot nitrogen supply. To increase end-of-life desorption efficiency, the Gen1 bed design was modified, and a Thermal Enhancement Cartridge Heater Modified (TECH Mod) bed was developed. Internal electric cartridge heaters in the new design to improve end-of-life desorption, and also permit in-bed tritium accountability (IBA) calibration measurements to be made without the use of process tritium. Additional enhancements implemented into the TECH Mod design are also discussed.« less

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. ...

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. ...

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.

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.

Installation Restoration Program. Remedial Investigation Report: Forbes Field Air National Guard Base, Topeka, Kansas

DTIC Science & Technology

1989-10-01

of toluene in the gastrointestinal tract occurs less readily. Toluene is distributed in the highest concentrations to adipose tissue followed by bone...were desorbed using a thermal desorption unit. Samples were injected by a desorber into a capillary column which was followed by quantification with...0.002 beryllium 0.1 0.001 cadmium 0.5 0.005 chromium 1 0.01 copper 1 0.01 lead 3 0.002 mercury 0.02 0.001 nickel 2 0.02 selenium 0.2 0.002 silver 0.5

Thermal Desorption/Ultraviolet Photolysis Process Technology Research, Test, and Evaluation Performed at the Naval Construction Battalion Center, Gulfport, Mississippi, for the USAF Installation Restoration Program. Volume 2

DTIC Science & Technology

1987-12-01

protection needs to be changed, then protection will be upgraded, or downgraded, as appropriate. 5 . Cartridges for air-purifying respirators will be...the gloves, the legs taped to the boots, and the hood to the respirator (if appropriate). All openings shall be sealed. 5 . The protective coveralls...placed next to the trash container. Note: Suits are to be removed in an inside out fashion. m. Station 5 - Respirator Removal A rack will be available to

Update on the direct n-n scattering experiment at the reactor YAGUAR

NASA Astrophysics Data System (ADS)

Stephenson, S. L.; Crawford, B. E.; Furman, W. I.; Lychagin, E. V.; Muzichka, A. Yu.; Nekhaev, G. V.; Sharapov, E. I.; Shvetsov, V. N.; Strelkov, A. V.; Levakov, B. G.; Lyzhin, A. E.; Chernukhin, Yu. I.; Howell, C. R.; Mitchell, G. E.; Tornow, W.; Showalter-Bucher, R. A.

2013-10-01

The first direct measurement of the 1S0 neutron-neutron scattering experiment using the YAGUAR aperiodic reactor at the Russian Federal Nuclear Center - All Russian Research Institute of Technical Physics has preliminary results. Thermal neutrons are scattered from a thermal neutron ``gas'' within the scattering chamber of the reactor and measured via time-of-flight. These initial results show an unexpectedly large thermal neutron background now understood to be from radiation-induced desorption within the scattering chamber. Analysis of the neutron time-of-flight spectra suggests neutron scattering from H2 and possibly H2O molecules. An experimental value for the desorption yield ηγ of 0.02 molecules/gamma agrees with modeled results. Techniques to reduce the effect of the nonthermal desorption will be presented. This work was supported in part by ISTC project No. 2286, Russia Found. Grant 01-02-17181, the US DOE grants Nos. DE-FG02-97-ER41042 and DE-FG02-97-ER41033, and by the US NSF through Award Nos. 0107263 and 0555652.

Application of an automatic thermal desorption-gas chromatography-mass spectrometry system for the analysis of polycyclic aromatic hydrocarbons in airborne particulate matter.

PubMed

Gil-Moltó, J; Varea, M; Galindo, N; Crespo, J

2009-02-27

The application of the thermal desorption (TD) method coupled with gas chromatography-mass spectrometry (GC-MS) to the analysis of aerosol organics has been the focus of many studies in recent years. This technique overcomes the main drawbacks of the solvent extraction approach such as the use of large amounts of toxic organic solvents and long and laborious extraction processes. In this work, the application of an automatic TD-GC-MS instrument for the determination of particle-bound polycyclic aromatic hydrocarbons (PAHs) is evaluated. This device offers the advantage of allowing the analysis of either gaseous or particulate organics without any modification. Once the thermal desorption conditions for PAH extraction were optimised, the method was verified on NIST standard reference material (SRM) 1649a urban dust, showing good linearity, reproducibility and accuracy for all target PAHs. The method has been applied to PM10 and PM2.5 samples collected on quartz fibre filters with low volume samplers, demonstrating its capability to quantify PAHs when only a small amount of sample is available.

Thermal desorption of PCB-contaminated soil with sodium hydroxide.

PubMed

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

2015-12-01

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

Occurrence of brominated flame retardants in black thermo cups and selected kitchen utensils purchased on the European market.

PubMed

Samsonek, J; Puype, F

2013-01-01

In order to screen for the presence of a recycled polymer waste stream from waste electric and electronic equipment (WEEE), a market survey was conducted on black plastic food-contact articles (FCA). An analytical method was applied combining X-ray fluorescence spectrometry (XRF) with thermal desorption gas chromatography coupled with mass spectrometry (thermal desorption GC-MS). Firstly, XRF spectrometry was applied to distinguish bromine-positive samples. Secondly, bromine-positive samples were submitted for identification by thermal desorption GC-MS. Generally, the bromine-positive samples contained mainly technical decabromodiphenyl ether (decaBDE). Newer types of BFRs such as tetrabromobisphenol A (TBBPA), tetrabromobisphenol A bis(2,3-dibromopropyl), ether (TBBPA-BDBPE) and decabromodiphenylethane (DBDPE), replacing the polybrominated diphenyleters (PBDEs) and polybrominated diphenyls (PBBs), were also identified. In none of the tested samples were PBBs or hexabromocyclododecane (HBCD) found. Polymer identification was carried out using Fourier-transformed infrared spectroscopy measurement (FTIR) on all samples. The results indicate that polypropylene-polyethylene copolymers (PP-PE) and mainly styrene-based food-contact materials, such as acrylonitrile-butadiene-styrene (ABS) have the highest risk of containing BFRs.

Rapid Analysis of Trace Drugs and Metabolites Using a Thermal Desorption DART-MS Configuration.

PubMed

Sisco, Edward; Forbes, Thomas P; Staymates, Matthew E; Gillen, Greg

2016-01-01

The need to analyze trace narcotic samples rapidly for screening or confirmatory purposes is of increasing interest to the forensic, homeland security, and criminal justice sectors. This work presents a novel method for the detection and quantification of trace drugs and metabolites off of a swipe material using a thermal desorption direct analysis in real time mass spectrometry (TD-DART-MS) configuration. A variation on traditional DART, this configuration allows for desorption of the sample into a confined tube, completely independent of the DART source, allowing for more efficient and thermally precise analysis of material present on a swipe. Over thirty trace samples of narcotics, metabolites, and cutting agents deposited onto swipes were rapidly differentiated using this methodology. The non-optimized method led to sensitivities ranging from single nanograms to hundreds of picograms. Direct comparison to traditional DART with a subset of the samples highlighted an improvement in sensitivity by a factor of twenty to thirty and an increase in reproducibility sample to sample from approximately 45 % RSD to less than 15 % RSD. Rapid extraction-less quantification was also possible.

In situ ionic liquid dispersive liquid-liquid microextraction and direct microvial insert thermal desorption for gas chromatographic determination of bisphenol compounds.

PubMed

Cacho, Juan Ignacio; Campillo, Natalia; Viñas, Pilar; Hernández-Córdoba, Manuel

2016-01-01

A new procedure based on direct insert microvial thermal desorption injection allows the direct analysis of ionic liquid extracts by gas chromatography and mass spectrometry (GC-MS). For this purpose, an in situ ionic liquid dispersive liquid-liquid microextraction (in situ IL DLLME) has been developed for the quantification of bisphenol A (BPA), bisphenol Z (BPZ) and bisphenol F (BPF). Different parameters affecting the extraction efficiency of the microextraction technique and the thermal desorption step were studied. The optimized procedure, determining the analytes as acetyl derivatives, provided detection limits of 26, 18 and 19 ng L(-1) for BPA, BPZ and BPF, respectively. The release of the three analytes from plastic containers was monitored using this newly developed analytical method. Analysis of the migration test solutions for 15 different plastic containers in daily use identified the presence of the analytes at concentrations ranging between 0.07 and 37 μg L(-1) in six of the samples studied, BPA being the most commonly found and at higher concentrations than the other analytes.

Application of thermal desorption for the identification of mercury species in solids derived from coal utilization.

PubMed

Rumayor, M; Diaz-Somoano, M; Lopez-Anton, M A; Martinez-Tarazona, M R

2015-01-01

The speciation of mercury is currently attracting widespread interest because the emission, transport, deposition and behaviour of toxic mercury species depend on its chemical form. The identification of these species in low concentrations is no easy task and it is even more complex in coal combustion products due to the fact that these products contain organic and mineral matter that give rise to broad peaks and make it difficult to carry out qualitative and quantitative analysis. In this work, a solution to this problem is proposed using a method based on thermal desorption. A sequential extraction procedure was employed for the comparison and validation of the method developed. Samples of fly ashes and soils were analyzed by both of these methods, and thermal desorption was found to be an appropriate technique for mercury speciation. Even in the case of low mercury contents, recovery percentages were close to 100%. The main mercury species identified in the samples studied were HgS and, to a lesser extent, HgO and HgSO4. In addition, although the presence of mercury complexes cannot be demonstrated, the desorption behaviour and sequential extraction results suggest that this element might be associated with the mineral matrix or with carbon particles in some of the solids. Copyright © 2014 Elsevier Ltd. All rights reserved.

Measurement of single crystal surface parameters

NASA Technical Reports Server (NTRS)

Swanson, L. W.; Bell, A. E.; Strayer, R. W.

1972-01-01

The sticking coefficient and thermal desorption spectra of Cs from the (110) plane of W was investigated. A sticking coefficient of unity for the monolayer region was measured for T 250 K. Several distinct binding states were observed in the thermal desorption spectrum. Work function and electron reflection measurements were made on the (110) and (100) crystal faces of Mo. Both LEED and Auger were used to determine the orientation and cleanliness of the crystal surfaces. The work function values obtained for the (110) and (100) planes of Mo were 4.92 and 4.18 eV respectively.

Insights into Acetone Photochemistry on Rutile TiO2(110). 1. Off-Normal CH3 Ejection from Acetone Diolate.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petrik, Nikolay G.; Henderson, Michael A.; Kimmel, Gregory A.

2015-06-04

Thermal- and photon-stimulated reactions of acetone co-adsorbed with oxygen on rutile TiO2(110) surface are studied with infrared reflection-adsorption spectroscopy (IRAS) combined with temperature programmed desorption and angle-resolved photon stimulated desorption. IRAS results show that n2-acetone diolate ((CH3)2COO) is produced via thermally-activated reactions between the chemisorbed oxygen with co-adsorbed acetone. Formation of acetone diolate is also consistent with 18O / 16O isotopic exchange experiments. During UV irradiation at 30 K, CH3 radicals are ejected from the acetone diolate with a distribution that is peaked at .-. +- 66 degrees from the surface normal along the azimuth (i.e. perpendicular to the rowsmore » of bridging oxygen and Ti5c ions). This distribution is also consistent with the orientation of the C–CH3 bonds in the n2-acetone diolate on TiO2(110). The acetone diolate peaks disappear from the IRAS spectra after UV irradiation and new peaks are observed and associated with n2-acetate. The data presented here demonstrate direct signatures of the proposed earlier 2-step mechanism for acetone photooxidation on TiO2(110)« less

Determination of residual solvents in bulk pharmaceuticals by thermal desorption/gas chromatography/mass spectrometry.

PubMed

Urakami, K; Saito, Y; Fujiwara, Y; Watanabe, C; Umemoto, K; Godo, M; Hashimoto, K

2000-12-01

Thermal desorption (TD) techniques followed by capillary GC/MS were applied for the analysis of residual solvents in bulk pharmaceuticals. Solvents desorbed from samples by heating were cryofocused at the head of a capillary column prior to GC/MS analysis. This method requires a very small amount of sample and no sample pretreatment. Desorption temperature was set at the point about 20 degrees C higher than the melting point of each sample individually. The relative standard deviations of this method tested by performing six consecutive analyses of 8 different samples were 1.1 to 3.1%, and analytical results of residual solvents were in agreement with those obtained by direct injection of N,N-dimethylformamide solution of the samples into the GC. This novel TD/GC/MS method was demonstrated to be very useful for the identification and quantification of residual solvents in bulk pharmaceuticals.

Thermochemical Properties of the Lattice Oxygen in W,Mn-Containing Mixed Oxide Catalysts for the Oxidative Coupling of Methane

NASA Astrophysics Data System (ADS)

Lomonosov, V. I.; Gordienko, Yu. A.; Sinev, M. Yu.; Rogov, V. A.; Sadykov, V. A.

2018-03-01

Mixed NaWMn/SiO2 oxide, samples containing individual components (Na, W, Mn) and their double combinations (Na-W, Na-Mn, W-Mn) supported on silica were studied by temperature programmed reduction (TPR) and desorption (TPD), and heat flow calorimetry during their reoxidation with molecular oxygen in pulse mode. The NaWMn/SiO2 mixed oxide was shown to contain two different types of reactive lattice oxygen. The weakly-bonded oxygen can be reversibly released from the oxide in a flow of inert gas in the temperature range of 575‒900°C, while the strongly-bonded oxygen can be removed during the reduction of the sample with hydrogen at 700-900°C. The measured thermal effect of oxygen consumption for these two oxygen forms are 185 and 350 kJ/mol, respectively. The amount of oxygen removed at reduction ( 443 μmol/g) considerably exceeded the amount desorbed in an inert gas flow ( 56 μmol/g). The obtained results suggest that the reversible oxygen desorption is due to the redox process in which manganese ions are involved, while during the temperature programmed reduction, mainly oxygen bonded with tungsten is removed.

Proceedings (1st) of the Topical Meeting on the Microphysics of Surfaces, Beams, and Adsorbates Held in Santa Fe, New Mexico on 4-6 February 1985.

DTIC Science & Technology

1985-12-18

by other molecules within the area of irradiation were desorbed with methods. Therefore, the laser thermal desorption techrique a single pulse . This...of 30 ns irradiated on W surfaces covered with D face temperature raised by a laser pulse . The problem asso- atoms. D, desorption time-of-flight was...surface region which cm- I.2411a The desorption yield (Y) dependence on the laser was not irradiated by the laser pulses . The diffusion coeffi

TMAP-7 simulation of D2 thermal release data from Be co-deposited layers

NASA Astrophysics Data System (ADS)

Baldwin, M. J.; Schwarz-Selinger, T.; Yu, J. H.; Doerner, R. P.

2013-07-01

The efficacy of (1) bake-out at 513 K and 623 K, and (2) thermal transient (10 ms) loading to up to 1000 K, is explored for reducing D inventory in 1 μm thick Be-D (D/Be ˜0.1) co-deposited layers formed at 323 K for experiment (1) and ˜500 K for experiment (2). D release data from co-deposits are obtained by thermal desorption and used to validate a model input into the Tritium Migration & Analysis Program 7 (TMAP). In (1), good agreement with experiment is found for a TMAP model encorporating traps of activation energies, 0.80 eV and 0.98 eV, whereas an additional 2 eV trap was required to model experiment (2). Thermal release is found to be trap limited, but simulations are optimal when surface recombination is taken into account. Results suggest that thick built-up co-deposited layers will hinder ITER inventory control, and that bake periods (˜1 day) will be more effective in inventory reduction than transient thermal loading.

Electron-driven and thermal chemistry during water-assisted purification of platinum nanomaterials generated by electron beam induced deposition

PubMed Central

Warneke, Jonas; Kopyra, Janina

2018-01-01

Focused electron beam induced deposition (FEBID) is a versatile tool for the direct-write fabrication of nanostructures on surfaces. However, FEBID nanostructures are usually highly contaminated by carbon originating from the precursor used in the process. Recently, it was shown that platinum nanostructures produced by FEBID can be efficiently purified by electron irradiation in the presence of water. If such processes can be transferred to FEBID deposits produced from other carbon-containing precursors, a new general approach to the generation of pure metallic nanostructures could be implemented. Therefore this study aims to understand the chemical reactions that are fundamental to the water-assisted purification of platinum FEBID deposits generated from trimethyl(methylcyclopentadienyl)platinum(IV) (MeCpPtMe3). The experiments performed under ultrahigh vacuum conditions apply a combination of different desorption experiments coupled with mass spectrometry to analyse reaction products. Electron-stimulated desorption monitors species that leave the surface during electron exposure while post-irradiation thermal desorption spectrometry reveals products that evolve during subsequent thermal treatment. In addition, desorption of volatile products was also observed when a deposit produced by electron exposure was subsequently brought into contact with water. The results distinguish between contributions of thermal chemistry, direct chemistry between water and the deposit, and electron-induced reactions that all contribute to the purification process. We discuss reaction kinetics for the main volatile products CO and CH4 to obtain mechanistic information. The results provide novel insights into the chemistry that occurs during purification of FEBID nanostructures with implications also for the stability of the carbonaceous matrix of nanogranular FEBID materials under humid conditions. PMID:29441253

Thermal release of D2 from new Be-D co-deposits on previously baked co-deposits

NASA Astrophysics Data System (ADS)

Baldwin, M. J.; Doerner, R. P.

2015-12-01

Past experiments and modeling with the TMAP code in [1, 2] indicated that Be-D co-deposited layers are less (time-wise) efficiently desorbed of retained D in a fixed low-temperature bake, as the layer grows in thickness. In ITER, beryllium rich co-deposited layers will grow in thickness over the life of the machine. Although, compared with the analyses in [1, 2], ITER presents a slightly different bake efficiency problem because of instances of prior tritium recover/control baking. More relevant to ITER, is the thermal release from a new and saturated co-deposit layer in contact with a thickness of previously-baked, less-saturated, co-deposit. Experiments that examine the desorption of saturated co-deposited over-layers in contact with previously baked under-layers are reported and comparison is made to layers of the same combined thickness. Deposition temperatures of ∼323 K and ∼373 K are explored. It is found that an instance of prior bake leads to a subtle effect on the under-layer. The effect causes the thermal desorption of the new saturated over-layer to deviate from the prediction of the validated TMAP model in [2]. Instead of the D thermal release reflecting the combined thickness and levels of D saturation in the over and under layer, experiment differs in that, i) the desorption is a fractional superposition of desorption from the saturated over-layer, with ii) that of the combined over and under -layer thickness. The result is not easily modeled by TMAP without the incorporation of a thin BeO inter-layer which is confirmed experimentally on baked Be-D co-deposits using X-ray micro-analysis.

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

PubMed

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

2017-06-01

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

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.

Ion-to-Neutral Ratios and Thermal Proton Transfer in Matrix-Assisted Laser Desorption/Ionization

NASA Astrophysics Data System (ADS)

Lu, I.-Chung; Chu, Kuan Yu; Lin, Chih-Yuan; Wu, Shang-Yun; Dyakov, Yuri A.; Chen, Jien-Lian; Gray-Weale, Angus; Lee, Yuan-Tseh; Ni, Chi-Kung

2015-07-01

The ion-to-neutral ratios of four commonly used solid matrices, α-cyano-4-hydroxycinnamic acid (CHCA), 2,5-dihydroxybenzoic acid (2,5-DHB), sinapinic acid (SA), and ferulic acid (FA) in matrix-assisted laser desorption/ionization (MALDI) at 355 nm are reported. Ions are measured using a time-of-flight mass spectrometer combined with a time-sliced ion imaging detector. Neutrals are measured using a rotatable quadrupole mass spectrometer. The ion-to-neutral ratios of CHCA are three orders of magnitude larger than those of the other matrices at the same laser fluence. The ion-to-neutral ratios predicted using the thermal proton transfer model are similar to the experimental measurements, indicating that thermal proton transfer reactions play a major role in generating ions in ultraviolet-MALDI.

Electron-stimulated reactions in nanoscale water films adsorbed on (alpha)-Al2O3(0001)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petrik, Nikolay G.; Kimmel, Gregory A.

2018-05-11

The radiation-induced decomposition and desorption of nanoscale amorphous solid water (D2O) films adsorbed on -Al2O3(0001) surface was studied at low temperature in ultrahigh vacuum using temperature programmed desorption (TPD) and electron stimulated desorption (ESD) with a mono-energetic, low energy electron source. ESD yields of molecular products ( D2, O2 and D¬2O) and the total sputtering yield increased with increasing D2O coverage up to ~15 water monolayers (i.e. ~15 1015 cm-2) to a coverage-independent level for thicker water films. Experiments with isotopically-layered water films (D2O and H2O) demonstrated that the highest water decomposition yields occurred at the interfaces of the nanoscalemore » water films with the alumina substrate and vacuum. However, the increased reactivity of the water/alumina interface is relatively small compared to the enhancements in the non-thermal reactions previously observed at the water/Pt(111) and water/TiO2(110) interfaces. We propose that the relatively low activity of Al2O3(0001) for the radiation-induced production of molecular hydrogen is associated with lower reactivity of this surface with hydrogen atoms, which are likely precursors for the molecular hydrogen.« less

Electron-stimulated reactions in nanoscale water films adsorbed on α-Al 2 O 3 (0001)

DOE PAGES

Petrik, Nikolay G.; Kimmel, Greg A.

2018-04-11

The radiation-induced decomposition and desorption of nanoscale amorphous solid water (D 2O) films adsorbed on an α-Al 2O 3(0001) surface was studied at low temperature in ultrahigh vacuum using temperature programmed desorption (TPD) and electron stimulated desorption (ESD) with a mono-energetic, low energy electron source. ESD yields of molecular products (D 2, O 2 and D 2O) and the total sputtering yield increased with increasing D 2O coverage up to ~15 water monolayers (i.e. ~15 x 10 15 cm -2) to a coverage-independent level for thicker water films. Experiments with isotopically-layered water films (D 2O and H 2O) demonstrated thatmore » the highest water decomposition yields occurred at the interfaces of the nanoscale water films with the alumina substrate and vacuum. However, the increased reactivity of the water/alumina interface is relatively small compared to the enhancements in the non-thermal reactions previously observed at the water/Pt(111) and water/TiO 2(110) interfaces. Here, we propose that the relatively low activity of Al 2O 3(0001) for the radiation-induced production of molecular hydrogen is associated with lower reactivity of this surface with hydrogen atoms, which are likely precursors for the formation of molecular hydrogen.« less

Electron-stimulated reactions in nanoscale water films adsorbed on α-Al 2 O 3 (0001)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petrik, Nikolay G.; Kimmel, Greg A.

The radiation-induced decomposition and desorption of nanoscale amorphous solid water (D 2O) films adsorbed on an α-Al 2O 3(0001) surface was studied at low temperature in ultrahigh vacuum using temperature programmed desorption (TPD) and electron stimulated desorption (ESD) with a mono-energetic, low energy electron source. ESD yields of molecular products (D 2, O 2 and D 2O) and the total sputtering yield increased with increasing D 2O coverage up to ~15 water monolayers (i.e. ~15 x 10 15 cm -2) to a coverage-independent level for thicker water films. Experiments with isotopically-layered water films (D 2O and H 2O) demonstrated thatmore » the highest water decomposition yields occurred at the interfaces of the nanoscale water films with the alumina substrate and vacuum. However, the increased reactivity of the water/alumina interface is relatively small compared to the enhancements in the non-thermal reactions previously observed at the water/Pt(111) and water/TiO 2(110) interfaces. Here, we propose that the relatively low activity of Al 2O 3(0001) for the radiation-induced production of molecular hydrogen is associated with lower reactivity of this surface with hydrogen atoms, which are likely precursors for the formation of molecular hydrogen.« less

Quantitative Detection of Trace Explosive Vapors by Programmed Temperature Desorption Gas Chromatography-Electron Capture Detector

PubMed Central

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

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

2014-07-25

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.

Investigation of the charge boost technology for the efficiency increase of closed sorption thermal energy storage systems

NASA Astrophysics Data System (ADS)

Rohringer, C.; Engel, G.; Köll, R.; Wagner, W.; van Helden, W.

2017-10-01

The inclusion of solar thermal energy into energy systems requires storage possibilities to overcome the gap between supply and demand. Storage of thermal energy with closed sorption thermal energy systems has the advantage of low thermal losses and high energy density. However, the efficiency of these systems needs yet to be increased to become competitive on the market. In this paper, the so-called “charge boost technology” is developed and tested via experiments as a new concept for the efficiency increase of compact thermal energy storages. The main benefit of the charge boost technology is that it can reach a defined state of charge for sorption thermal energy storages at lower temperature levels than classic pure desorption processes. Experiments are conducted to provide a proof of principle for this concept. The results show that the charge boost technology does function as predicted and is a viable option for further improvement of sorption thermal energy storages. Subsequently, a new process application is developed by the author with strong focus on the utilization of the advantages of the charge boost technology over conventional desorption processes. After completion of the conceptual design, the theoretical calculations are validated via experiments.

Molecular Sieve Bench Testing and Computer Modeling

NASA Technical Reports Server (NTRS)

Mohamadinejad, Habib; DaLee, Robert C.; Blackmon, James B.

1995-01-01

The design of an efficient four-bed molecular sieve (4BMS) CO2 removal system for the International Space Station depends on many mission parameters, such as duration, crew size, cost of power, volume, fluid interface properties, etc. A need for space vehicle CO2 removal system models capable of accurately performing extrapolated hardware predictions is inevitable due to the change of the parameters which influences the CO2 removal system capacity. The purpose is to investigate the mathematical techniques required for a model capable of accurate extrapolated performance predictions and to obtain test data required to estimate mass transfer coefficients and verify the computer model. Models have been developed to demonstrate that the finite difference technique can be successfully applied to sorbents and conditions used in spacecraft CO2 removal systems. The nonisothermal, axially dispersed, plug flow model with linear driving force for 5X sorbent and pore diffusion for silica gel are then applied to test data. A more complex model, a non-darcian model (two dimensional), has also been developed for simulation of the test data. This model takes into account the channeling effect on column breakthrough. Four FORTRAN computer programs are presented: a two-dimensional model of flow adsorption/desorption in a packed bed; a one-dimensional model of flow adsorption/desorption in a packed bed; a model of thermal vacuum desorption; and a model of a tri-sectional packed bed with two different sorbent materials. The programs are capable of simulating up to four gas constituents for each process, which can be increased with a few minor changes.

Pilot-Scale Silicone Process for Low-Cost Carbon Dioxide Capture. Final Scientific/Technical Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hancu, Dan; Wood, Benjamin; Genovese, Sarah

GE Global Research has developed, over the last 8 years, a platform of cost effective CO 2 capture technologies based on a non-aqueous aminosilicone solvent (GAP-1m). As demonstrated in a previous funded DOE project (DE-FE0007502), the GAP-1m solvent has increased CO 2 working capacity, lower volatility and corrosivity than the benchmark aqueous amine technology. The current report describes the cooperative program between GE Global Research (GE GRC), and the National Carbon Capture Center (NCCC) to design, construct, and operate a pilot-scale process using GAP-1m solvent to demonstrate its performance at 0.5 MWe. (i) Performance of the GAP-1m solvent was demonstratedmore » in a 0.5 MWe pilot with real flue gas for over 900 hrs. of operation using two alternative desorption designs: a Continuous Stirred Tank Reactor (CSTR), and a Steam Stripper Column (SSC). The CSTR is a one-stage separation unit with reduced space requirements, and capital cost. The alternative is a multi-stage separation column, with improved desorption efficiency. Testing the two desorber options allowed us to identify the most cost effective, and space efficient desorber solution. (ii) CSTR Campaign: The CSTR desorber unit was designed, fabricated and integrated with the pilot solvent test unit (PSTU), replacing the PSTU Steam Stripper Column at NCCC. Solvent management and waste water special procedures were implemented to accommodate operation of the non-aqueous solvent in the PSTU. Performance of the GAP-1m solvent with the CSTR was demonstrated for over 500 hrs. while varying temperature of the desorption (230 – 265 oF), solvent circulation rate (GAP-1m : CO 2 (molar) = 1.5 – 4), and flue gas flow rates (0.2 – 0.5 MWe). Solvent carry-over in the CO 2 product was minimized by maintaining water content below 5 wt.%, and desorption pressure at 7 psig. CO 2 capture efficiency achieved was 95% at 0.25 MWe (GAP-1m : CO 2 = 4 (molar), 230 oF desorption), and 65% at 0.5 MWe (GAP-1m : CO 2 (molar) = 1.5, 248 oF). Solvent loss was dominated by thermal degradation of the rich solvent. (iii) Steam Stripper Column Campaign: Higher expected cost of the solvent vs. aqueous amines makes solvent management a top priority to maintain the low cost for the process. During the testing of the GAP-1m solvent with the CSTR, thermal degradation of the rich solvent was found to be the main mechanism in solvent loss. Small amounts of water in the working solution were found to be an effective way to enable steam stripping, thereby lowering desorption temperature, and hence reducing thermal degradation. Steam stripping also increased working capacity by 30% due to a more efficient desorption. The concept was first tested in a glass stripping column (lab scale, GE GRC), optimized in a continuous bench scale system (2 kWe, GE GRC), and demonstrated in a 0.5 MWe PSTU at NCCC. No special system modifications were required to the PSTU to accommodate the testing of the non-aqueous GAP-1 solvent with the regenerator column. SSC was found to be more robust towards solvent entrainment (H 2O < 35 wt.%). 90 – 95% CO 2 capture efficiency was achieved under stoichiometric conditions at 0.5 MWe (235 oF desorption, 2 psig and 19 wt. % H 2O). Both CO 2 capture efficiency and specific duty reached optimum conditions at 18 wt.% H 2O. Low amine degradation (< 0.05 wt.%/day) was recorded over 350 hrs. of operation. Controlled water addition to GAP-1m solvent decreased the desorption temperature, thermal degradation, and improved the CO 2 working capacity due to more efficient absorption and desorption processes. Under these conditions, the GAP-1m solvent exhibited a 25% increased working capacity, and 10% reduction in specific steam duty vs. MEA, at 10 oF lower desorption temperature. (iv) Techno-economic Analysis: The pilot-scale PSTU engineering data were used to update the capture system process models, and the techno-economic analysis was performed for a 550 MW coal fired power plant. The 1st year CO 2 removal cost for the aminosilicone-based carbon-capture process was evaluated at $48/ton CO 2 using the steam stripper column. This is a 20% reduction compared to MEA, primarily due to lower overall capital cost. CO 2 cost using the CSTR desorber is dominated by the economics of the solvent make-up. The steam stripper desorber is the preferred unit operation due to a more efficient desorption, and reduced solvent make-up rate. Further reduction in CO 2 capture cost is expected by lowering the manufacturing cost of the solvent, implementing flowsheet optimization and/or implementing the next generation aminosilicone solvent with improved stability and increased CO 2 working capacity.« less

Plume characteristics and dynamics of UV and IR laser-desorbed oligonucleotides.

PubMed

Merrigan, Tony L; Timson, David J; Hunniford, C Adam; Catney, Martin; McCullough, Robert W

2012-05-01

Laser desorption of dye-tagged oligonucleotides was studied using laser-induced fluorescence imaging. Desorption with ultra violet (UV) and infra-red (IR) lasers resulted in forward directed plumes of molecules. In the case of UV desorption, the initial shot desorbed approximately seven-fold more material than subsequent shots. In contrast, the initial shot in IR desorption resulted in the ejection of less material compared to subsequent shots and these plumes had a component directed along the path of the laser. Thermal equilibrium of the molecules in the plume was achieved after approximately 25 μs with a spread in molecular temperature which was described by a modified Maxwell-Boltzmann equation. Copyright © 2012 Elsevier B.V. All rights reserved.

Numerical comparison of hydrogen desorption behaviors of metal hydride beds based on uranium and on zirconium-cobalt

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kyoung, S.; Yoo, H.; Ju, H.

2015-03-15

In this paper, the hydrogen delivery capabilities of uranium (U) and zirconium-cobalt (ZrCo) are compared quantitatively in order to find the optimum getter materials for tritium storage. A three-dimensional hydrogen desorption model is applied to two identically designed cylindrical beds with the different materials, and hydrogen desorption simulations are then conducted. The simulation results show superior hydrogen delivery performance and easier thermal management capability for the U bed. This detailed analysis of the hydrogen desorption behaviors of beds with U and ZrCo will help to identify the optimal bed material, bed design, and operating conditions for the storage and deliverymore » system in ITER. (authors)« less

ε-Polylysine-based thermo-responsive adsorbents for immunoglobulin adsorption-desorption under mild conditions.

PubMed

Maruyama, Masashi; Shibuya, Keisuke

2017-08-22

Thermo-responsive adsorbents for immunoglobulin G (IgG) employing ε-polylysine (EPL) as a polymer backbone were developed. The introduction of mercaptoethylpyridine (MEP) as an IgG-binding ligand and hydrophobization of side chains afforded thermo-responsive IgG adsorbents, whose thermo-responsive IgG desorption ratio was up to 88% (EPL/MEP derivative 3m). The changes in surface densities of active MEP groups, which are caused by thermal conformational changes of the adsorbents, play key roles for IgG desorption. Although a trade-off of IgG adsorption capacity and IgG desorption ratio was observed, the present study offers a novel molecular design for thermo-responsive adsorbents with high synthetic accessibility and potentially low toxicity.

Multivariate analysis of progressive thermal desorption coupled gas chromatography-mass spectrometry.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Van Benthem, Mark Hilary; Mowry, Curtis Dale; Kotula, Paul Gabriel

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 varymore » 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.« less

Photon-induced Processing of Interstellar Ices in the Laboratory. Focus on Their Non-thermal Desorption.

NASA Astrophysics Data System (ADS)

Martin-Domenech, Rafael; Munoz Caro, Guillermo; Cruz-Diaz, Gustavo A.; Oberg, Karin I.

2018-06-01

Some of the processes that take place in the interstellar medium (ISM)can be simulated in laboratories on Earth under astrophysically relevant conditions. For example, the energetic processing of the ice mantles that accrete on top of dust grains in the coldest regions of the ISM, leading to the production of new species and their desorption to the gas phase. In particular, observation of complex organic molecules (COMs) in cold interstellar environments stress the need for not only a solid state formation but also for non-thermal desorption mechanisms that can account for the observed abundances in regions where thermal desorption is inhibited. Laboratory Astrophysics can be used to test different non-thermal desorption processes and extract yields than can be extrapolated to the astrophysical scenario with theoretical models. 0th generation COMs like CH3OH and H2CO can be formed at very low temperatures. In this talk, we present laboratory simulations of the UV photoprocessing of a binary ice mixture composed by water (the main component of astrophysical ices) and methane. Formation of CO, CO2, CH3OH and H2CO was confirmed by IR spectroscopy and subsequent TPD. At the same time, photodesorption of CO and H2CO was detected by means of a Quadrupole Mass Spectrometer, with yields on the order of 10-4 and 10-5 molecules per incident photon, respectively. In general, photodesorption can take place through a direct mechanism, where the absorbing molecule (or its photofragments) are desorbed; or through an indirect mechanism where the absorbed energy is transferred to a surface molecule which is the one finally desorbing. In the case of photoproducts, the evolution of the photodesorption yield gives information on the photodesorption mechanism: a constant photodesorption yield is observed when the photoproducts are desorbed right after their formation; while an increasing yield is measured when the photoproducts are desorbed later after energy transfer from another absorbing molecule, allowing to roughly distinguish between different mechanisms.

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.

Comparison between different adsorption-desorption kinetics schemes in two dimensional lattice gas

NASA Astrophysics Data System (ADS)

Huespe, V. J.; Belardinelli, R. E.; Pereyra, V. D.; Manzi, S. J.

2017-12-01

Monte Carlo simulation is used to study the adsorption-desorption kinetics in the framework of the kinetic lattice-gas model. Three schemes of the so-called hard dynamics and five schemes of the so called soft dynamics were used for this purpose. It is observed that for the hard dynamic schemes, the equilibrium and non-equilibrium observable, such as adsorption isotherms, sticking coefficients, and thermal desorption spectra, have a normal or physical sustainable behavior. While for the soft dynamics schemes, with the exception of the transition state theory, the equilibrium and non-equilibrium observables have several problems.

Determination of 1-chloro-4-[2,2,2-trichloro-1-(4-chlorophenyl)ethyl]benzene and related compounds in marine pore water by automated thermal desorption-gas chromatography/mass spectrometry using disposable optical fiber

USGS Publications Warehouse

Eganhouse, Robert P.; DiFilippo, Erica L

2015-01-01

A method is described for determination of ten DDT-related compounds in marine pore water based on equilibrium solid-phase microextraction (SPME) using commercial polydimethylsiloxane-coated optical fiber with analysis by automated thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS). Thermally cleaned fiber was directly exposed to sediments and allowed to reach equilibrium under static conditions at the in situ field temperature. Following removal, fibers were rinsed, dried and cut into appropriate lengths for storage in leak-tight containers at -20°C. Analysis by TD-GC/MS under full scan (FS) and selected ion monitoring (SIM) modes was then performed. Pore-water method detection limits in FS and SIM modes were estimated at 0.05-2.4ng/L and 0.7-16pg/L, respectively. Precision of the method, including contributions from fiber handling, was less than 10%. Analysis of independently prepared solutions containing eight DDT compounds yielded concentrations that were within 6.9±5.5% and 0.1±14% of the actual concentrations in FS and SIM modes, respectively. The use of optical fiber with automated analysis allows for studies at high temporal and/or spatial resolution as well as for monitoring programs over large spatial and/or long temporal scales with adequate sample replication. This greatly enhances the flexibility of the technique and improves the ability to meet quality control objectives at significantly lower cost.

Evaluation of Water Repellency in Petroleum Drilling Cuttings Treated by Thermal Desorption: Implications for Use in Construction and Agriculture

NASA Astrophysics Data System (ADS)

Domínguez-Rodríguez, Verónica I.; Guzmán-Osorio, Francisco J.; Adams Schroeder, Randy H.; Bautista-Margulis, Raúl G.

2010-05-01

Thermal desorption is one of many methods used for the remediation of hydrocarbon contaminated soils and similar materials. It has several advantages over competing technologies, especially with respect to treatment times. While the biological treatment of contaminated soils may take several months depending principally on the type of hydrocarbons and starting concentration, thermal desorption typically takes less than one month, depending on the treatment capacities of the equipment involved, and the volume of material requiring treatment. In the petroleum producing region of southeastern Mexico, this has been one of the principal methods used for the treatment of drilling cuttings, due mostly to the short time required. As with most remediation projects, as well as in the treatment of exploration and production (E&P) wastes, the criteria used to consider the remediation finalized is the concentration of hydrocarbons in the treated material. This is based on the supposition that at some (relatively low) hydrocarbon concentration, the toxicological affects are reduced to acceptable levels. However, little attention has been paid to the physical-chemical properties of supposedly treated material, which may suffer from water repellency, especially in thermal treatment methods. This could greatly reduce the options for final use of treated materials, especially to support plant growth. Conversely, there may be some construction uses of treated material in which some water repellence could be beneficial (caps for land fills, for example). Considering the relevance of the physical-chemical impacts of petroleum on soil and similar materials, we felt it was important to evaluate the efficiency of the principal method used to treat E&P wastes in Mexico (thermal desporption) based on these factors. In this study different operating conditions (temperature and residence time) of a sub-pilot scale thermal desorption unit were evaluated with respect not only to reduction in hydrocarbon concentration, but also based on water repellency. To our knowledge this is the first study of this type. Water repellency severity was measured in petroleum drilling cuttings which had been treated by thermal desorption to reduce the concentration of total petroleum hydrocarbons (TPHs). The initial TPH concentration in the untreated material was 16850mg/Kg (dry). The prototype batch rotary oven used in this study was operated at 25 rpm, at three temperatures and three treatment times: at 150, 200, and 300°C, for 10, 15, and 20 minutes. Four of the nine treatments complied with the Mexican environmental norm (TPH less than 3000 mg/Kg), these being: at 200°C for 20 minutes and at 300°C for 10, 15 and 20 minutes. The treatments at 150°C resulted in a TPH reduction insufficient to comply with Mexican norm, and also resulted in high MED values (3,46 - 3,67). At 200°C, the decrease in repellency was directly proportional to the treatment time (r=-0,950), with a final value of MED=2,61 after 20 minutes. At 300°C, an increase in water repellency was observed to be directly proportional to the treatment time (r=0,9997), with a final value of MED=3,73 (severe repellence) after 20 minutes. This may be due to the partial combustion (rather than only desorption) of hydrocarbons at this temperature, and their deposition on soil surfaces. Based on these observations, operating conditions of 200°C for 20 minutes are recommended to achieve effective thermal desorption while reducing water repellency in the treated material. If a final material with more severe water repellency is desired for use in construction, a higher operation temperature is required (300°C) for at least 15-20 minutes.

Desorption Kinetics of Methanol, Ethanol, and Water from Graphene

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 alignmentmore » 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.« less

Desorption kinetics of methanol, ethanol, and water from graphene.

PubMed

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 monolayer (ML)) the initial desorption leading edges are aligned but then fall out of alignment at higher temperatures. For thicker water layers (10-100 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 nonalignment 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.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, R. Scott; Kay, Bruce D.

The desorption kinetics for benzene and cyclohexane from a graphene covered Pt(111) surface were investigated using temperature programmed desorption (TPD). The benzene desorption spectra show well-resolved monolayer and multilayer desorption peaks. The benzene monolayer TPD spectra have the same desorption peak temperature and have line shapes which are consistent with first-order desorption kinetics. For benzene coverages greater than 1 ML, the TPD spectra align on a common leading edge which is consistent with zero-order desorption. An inversion analysis of the monolayer benzene TPD spectra yielded a desorption activation energy of 54 ± 3 kJ/mol with a prefactor of 1017 ±more » 1 s-1. The TPD spectra for cyclohexane also have well-resolved monolayer and multilayer desorption features. The desorption leading edges for the monolayer and the multilayer TPD spectra are aligned indicating zero-order desorption kinetics in both cases. An Arrhenius analysis of the monolayer cyclohexane TPD spectra yielded a desorption activation energy of 53.5 ± 2 kJ/mol with a prefactor of 1016 ± 1 ML s-1.« less

Helium self-trapping and diffusion behaviors in deformed 316L stainless steel exposed to high flux and low energy helium plasma

NASA Astrophysics Data System (ADS)

Gong, Yihao; Jin, Shuoxue; Zhu, Te; Cheng, Long; Cao, Xingzhong; You, Li; Lu, Guanghong; Guo, Liping; Wang, Baoyi

2018-04-01

A large number of dislocation networks were introduced in to 316L stainless steel by cold rolling. Subsequently, low energy (40 eV) helium ions were implanted by exposing the steel to helium plasma. Thermal desorption and positron annihilation spectroscopy were used to study the behavior of helium in the presence of dislocations, with emphasis on helium self-trapping and migration behaviors. Helium desorption behaviour from different helium trapping states was measured by the thermal desorption spectroscopy. Most of the helium desorbed from the He m V n clusters, and the corresponding desorption peak is located at ~650 K. The desorption peak from helium-dislocation clusters (He m D) is at approximately 805 K. The effect of annealing on the defect evolution was investigated by positron annihilation spectroscopy. For the specimen exposed to helium plasma without displacement damage, the increment of S parameter meant the existence of helium self-trapping behavior (He m V n ). Helium atoms could diffuse two to three orders of magnitude deeper than the implantation depth calculated by SRIM. The diffusing helium atoms were gradually trapped by dislocation lines and formed He m D. Elevated temperatures enhance the self-trapping behavior and cause helium atoms to dissociate/desorb from the He m V n clusters, increasing the S parameters at 473-673 K. The gradual recovery of vacancies in the He m V n clusters decreased the S parameter above 673 K.

Leidenfrost phenomenon-assisted thermal desorption (LPTD) and its application to open ion sources at atmospheric pressure mass spectrometry.

PubMed

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.

Deuterium trapping in tungsten

NASA Astrophysics Data System (ADS)

Poon, Michael

Tungsten is one of the primary material candidates being investigated for use in the first-wall of a magnetic confinement fusion reactor. An ion accelerator was used to simulate the type of ion interaction that may occur at a plasma-facing material. Thermal desorption spectroscopy (TDS) was the primary tool used to analyze the effects of the irradiation. Secondary ion mass spectroscopy (SIMS) was used to determine the distribution of trapped D in the tungsten specimen. The tritium migration analysis program (TMAP) was used to simulate thermal desorption profiles from the D depth distributions. Fitting of the simulated thermal desorption profiles with the measured TDS results provided values of the D trap energies. Deuterium trapping in single crystal tungsten was studied as a function of the incident ion fluence, ion flux, irradiation temperature, irradiation history, and surface impurity levels during irradiation. The results show that deuterium was trapped at vacancies and voids. Two deuterium atoms could be trapped at a tungsten vacancy, with trapping energies of 1.4 eV and 1.2 eV for the first and second D atoms, respectively. In a tungsten void, D is trapped as atoms adsorbed on the inner walls of the void with a trap energy of 2.1 eV, or as D2 molecules inside the void with a trap energy of 1.2 eV. Deuterium trapping in polycrystalline tungsten was also studied as a function of the incident fluence, irradiation temperature, and irradiation history. Deuterium trapping in polycrystalline tungsten also occurs primarily at vacancies and voids with the same trap energies as in single crystal tungsten; however, the presence of grain boundaries promotes the formation of large surface blisters with high fluence irradiations at 500 K. In general, D trapping is greater in polycrystalline tungsten than in single crystal tungsten. To simulate mixed materials comprising of carbon (C) and tungsten, tungsten specimens were pre-irradiated with carbon ions prior to D irradiation. Deuterium trapping could be characterized by three regimes: (i) enhanced D retention in a graphitic film formed by the C+ irradiation; (ii) decreased D retention in a modified tungsten-carbon layer; and (iii) D retention in pure tungsten.

The adsorption and thermal decomposition of PH 3 on Si(111)-(7 × 7)

NASA Astrophysics Data System (ADS)

Taylor, P. A.; Wallace, R. M.; Choyke, W. J.; Yates, J. T.

1990-11-01

The adsorption of PH 3, on Si(111)-(7 × 7) has been studied by Auger electron spectroscopy and temperature programmed desorption. PH 3 was found to exhibit two kinds of behavior on the surface. A small surface coverage of molecularly adsorbed PH 3 desorbs without any dissociative surface chemistry. For the majority of the adsorbed PH x species (3 ⩾ x ⩾ 1) dissociation occurs to form P(a) and H(a). At 120 K, PH 3 initially adsorbs as the reactive species with a sticking coefficient of S ≅ 1 up to ˜75% saturation. The reactive PH x species surface concentration saturates at (1.9 ± 0.3) × 10 14 PH x cm -2. Surface H(a), produc thermal decomposition, desorbs as H 2(g) at T > 700 K., and P(a) desorbs as P 2(g) at T > 900 K. Capping the Si-dangling bonds with atomic deuterium prevents PH 3 adsorption, indicating that the dangling bonds are the PH 3 adsorption sites. Isotopic studies involving Si-D surface species mixed with adsorbed PH x species indicate that PH 3 desorption does not occur through a recombination process. Finally, additional PH 3 may be adsorbed if the surface hydrogen produced by dissociation of PH 3 is removed. Evidence for P penetration into bulk Si(111) at 875 K is presented.

Minimizing thermal degradation in gas chromatographic quantitation of pentaerythritol tetranitrate.

PubMed

Lubrano, Adam L; Field, Christopher R; Newsome, G Asher; Rogers, Duane A; Giordano, Braden C; Johnson, Kevin J

2015-05-15

An analytical method for establishing calibration curves for the quantitation of pentaerythriol tetranitrate (PETN) from sorbent-filled thermal desorption tubes by gas chromatography with electron capture detection (TDS-GC-ECD) was developed. As PETN has been demonstrated to thermally degrade under typical GC instrument conditions, peaks corresponding to both PETN degradants and molecular PETN are observed. The retention time corresponding to intact PETN was verified by high-resolution mass spectrometry with a flowing atmospheric pressure afterglow (FAPA) ionization source, which enabled soft ionization of intact PETN eluting the GC and subsequent accurate-mass identification. The GC separation parameters were transferred to a conventional GC-ECD instrument where analytical method-induced PETN degradation was further characterized and minimized. A method calibration curve was established by direct liquid deposition of PETN standard solutions onto the glass frit at the head of sorbent-filled thermal desorption tubes. Two local, linear relationships between detector response and PETN concentration were observed, with a total dynamic range of 0.25-25ng. Published by Elsevier B.V.

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

24-HOUR DIFFUSIVE SAMPLING OF 1,3-BUTADIENE IN AIR ONTO CARBONPAK X SOLID ADSORBENT WITH THEMAL DESORPTION/GC/MS ANALYSIS - FEASIBILITY STUDIES

EPA Science Inventory

Diffusive sampling of 1,3-butadiene for 24 hours onto the graphitic adsorbent Carbopack X contained in a stainless steel tube badge (6.3 mm OD, 5 mm ID, and 90 mm in length) with analysis by thermal desorption/GC/MS has been evaluated in controlled tests. A test matrix of 42 tr...

On-fiber furan formation from volatile precursors: a critical example of artefact formation during Solid-Phase Microextraction.

PubMed

Adams, An; Van Lancker, Fien; De Meulenaer, Bruno; Owczarek-Fendor, Agnieszka; De Kimpe, Norbert

2012-05-15

For the analysis of furan, a possible carcinogen formed during thermal treatment of food, Solid-Phase Microextraction (SPME) is a preferred and validated sampling method. However, when volatile furan precursors are adsorbed on the carboxen/PDMS fiber, additional amounts of furan can be formed on the fiber during thermal desorption, as shown here for 2-butenal and furfural. No significant increase in furan amounts was found upon heating the furan precursor 2-butenal, indicating that the furan amounts formed during precursor heating experiments are negligible as compared to the additional amounts of furan formed during fiber desorption. This artefactual furan formation increased with increasing desorption time, but especially with increasing desorption temperature. Although this effect was most pronounced on the Carboxen/PDMS SPME-fiber, it was also noted on two other SPME-fibers tested (PDMS and DVB/Carboxen/PDMS). The general impact on furan data from food and model systems in literature will depend on the amounts of volatile precursors present, but will probably remain limited. However, considering the importance of this worldwide food contaminant, special care has to be taken during SPME-analysis of furan. Especially when performing precursor studies, static headspace sampling should preferably be applied for furan analysis. Copyright © 2012 Elsevier B.V. All rights reserved.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

2016-03-03

The desorption kinetics for Ar, Kr, Xe, N2, O2, CO, methane, ethane, and propane from grapheme 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 multi- layer 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 notmore » align (for coverages < 2 ML). The non-alignment 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.« less

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

2016-03-03

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.

Analysis of ecstasy in oral fluid by ion mobility spectrometry and infrared spectroscopy after liquid-liquid extraction.

PubMed

Armenta, Sergio; Garrigues, Salvador; de la Guardia, Miguel; Brassier, Judit; Alcalà, Manel; Blanco, Marcelo

2015-03-06

We developed and evaluated two different strategies for determining abuse drugs based on (i) the analysis of saliva by ion mobility spectrometry (IMS) after thermal desorption and (ii) the joint use of IMS and infrared (IR) spectroscopy after liquid-liquid microextraction (LLME) to enable the sensitivity-enhanced detection and double confirmation of ecstasy (MDMA) abuse. Both strategies proved effective for the intended purpose. Analysing saliva by IMS after thermal desorption, which provides a limit of detection (LOD) of 160μgL(-1), requires adding 0.2M acetic acid to the sample and using the truncated negative second derivative of the ion mobility spectrum. The joint use of IMS and IR spectroscopy after LLME provides an LOD of 11μgL(-1) with the former technique and 800μgL(-1) with the latter, in addition to a limit of confirmation (LOC) of 1.5mgL(-1). Using IMS after thermal desorption simplifies the operational procedure, and using it jointly with IR spectroscopy after LLME allows double confirmation of MDMA abuse with two techniques based on different principles (viz., IMS drift times and IR spectra). Also, it affords on-site analyses, albeit at a lower throughput. Copyright © 2015 Elsevier B.V. All rights reserved.

Demonstration of Laser Induced Acoustic Desoprtion - Chemical Ionization Mass Spectrometry (LIAD-CIMS) for Fragment-Free Measurements of Organic Aerosol Molecular Composition

NASA Astrophysics Data System (ADS)

Browne, E. C.; Abdelhamid, A.; Berry, J.; Alton, M.

2017-12-01

Organic compounds account for a significant portion of fine atmospheric aerosol. Current analytical techniques have provided insights on organic aerosol (OA) sources, composition, and chemical modification pathways. Despite this knowledge, large uncertainties remain and hinder our understanding of aerosol impacts on climate, air quality, and health. Measuring OA composition is challenging due to the complex chemical composition and the wide variation in the properties (e.g., vapor pressure, solubility, reactivity) of organic compounds. In many current measurement techniques, the ability to chemically resolve and quantify OA components is complicated by molecular decomposition, matrix effects, and/or preferential ionization mechanisms. Here, we utilize a novel desorption technique, laser induced acoustic desorption (LIAD), that generates fragment-free, neutral gas-phase molecules. We couple LIAD with a high-resolution chemical ionization mass spectrometer (CIMS) to provide molecular composition OA measurements. Through a series of laboratory experiments, we demonstrate the ability of this technique to measure large, thermally labile species without fragmentation/thermal decomposition. We discuss quantification and detection limits of this technique. We compare LIAD-CIMS measurements with thermal desorption-CIMS measurements using off-line measurements of ambient aerosol collected in Boulder, CO. Lastly, we discuss future development for on-line measurements of OA using LIAD-CIMS.

High heating rate thermal desorption for molecular surface sampling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ovchinnikova, Olga S.; Van Berkel, Gary J.

2016-03-29

A method for analyzing a sample having at least one analyte includes the step of heating the sample at a rate of at least 10.sup.6 K/s to thermally desorb at least one analyte from the sample. The desorbed analyte is collected. The analyte can then be analyzed.

Desorption of Benzene, 1,3,5-Trifluorobenzene, and Hexafluorobenzene from a Graphene Surface: The Effect of Lateral Interactions on the Desorption Kinetics.

PubMed

Smith, R Scott; Kay, Bruce D

2018-05-17

The desorption of benzene, 1,3,5-trifluorobenzene (TFB), and hexafluorobenzene (HFB) from a graphene covered Pt(111) substrate was investigated using temperature-programmed desorption (TPD). All three species have well-resolved monolayer and second-layer desorption peaks. The desorption spectra for submonolayer coverages of benzene and HFB are consistent with first-order desorption kinetics. In contrast, the submonolayer TPD spectra for TFB align on a common leading-edge, which is indicative of zero-order desorption kinetics. The desorption behavior of the three molecules can be correlated with the strength of the quadrupole moments. Calculations (second-order Møller-Plesset perturbation and density functional theory) show that the potential minimum for coplanar TFB dimers is more than a factor of 2 greater than that for either benzene or HFB dimers. The calculations support the interpretation that benzene and HFB are less likely to form the two-dimensional islands that are needed for submonolayer zero-order desorption kinetics.

Enthalpy of sublimation as measured using a silicon oscillator

NASA Astrophysics Data System (ADS)

Shakeel, Hamza; Pomeroy, J. M.

In this study, we report the enthalpy of sublimation of common gases (nitrogen, oxygen, argon, carbon dioxide, neon, krypton, xenon, and water vapor) using a large area silicon oscillator with a sub-ng (~0.027 ng/cm2) mass sensitivity. The double paddle oscillator design enables high frequency stability (17 ppb) at cryogenic temperatures and provides a consistent technique for enthalpy measurements. The enthalpies of sublimation are derived from the rate of mass loss during programmed thermal desorption and are detected as a change in the resonance frequency of the self-tracking oscillator. These measured enthalpy values show excellent agreement with the accepted literature values.

Hydrogen isotope transport across tungsten surfaces exposed to a fusion relevant He ion fluence

NASA Astrophysics Data System (ADS)

Baldwin, M. J.; Doerner, R. P.

2017-07-01

Tungsten targets are exposed to controlled sequences of D2 and He, and He and D2 plasma in the Pisces-A linear plasma device, with a view to studying the outward and inward transport of D across a He implanted surface, using thermal desorption mass spectrometry. Differences in transport are interpreted from changes in peak desorption temperature and amplitude for D2 release, compared against that of control targets exposed to just D2 plasma. Desorption data are modeled with Tmap-7 to infer the nature by which He leads to the ‘reduced inventory’ effect for H isotope uptake. A dual segment (surface-30 nm, bulk) W Tmap-7 model is developed, that simulates both plasma exposure and thermal desorption. Good agreement between desorption data and model is found for D2 release from control targets provided that the implanted flux is reduced, similar to that reported by others. For He affected release, the H isotope transport properties of the surface segment are adjusted away from control target bulk values during the computation. Modeling that examines outward D transport through the He implanted layer suggests that a permeation barrier is active, but bubble induced porosity is insufficient to fully explain the barrier strength. Moderately increased diffusional migration energy in the model over the He affected region, however, gives a barrier strength consistent with experiment. The same model, applied to inward transport, predicts the reduced inventory effect, but a further reduction in the implanted D flux is necessary for precise agreement.

High field 27Al MAS NMR and TPD studies of active sites in ethanol dehydration using thermally treated transitional aluminas as catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Jian Zhi; Xu, Suochang; Kwak, Ja Hun

High field quantitative 27Al MAS NMR and temperature programmed desorption (TPD) of ethanol are used to study the surface and phase transformation of gamma-Al2O3 during calcination in the temperature range of 500 to 1300 degrees C. Following ethanol adsorption, ethylene is generated during TPD with a desorption temperature > 200 degrees C. With increasing calcination temperature prior to TPD, the amount of ethylene produced decreases monotonically. Significantly, 27Al MAS NMR reveals that the amount of penta-coordinate Al3+ ions (Lewis acid sites) also decreases with increasing calcination temperature. In fact, a strong correlation between the amount of penta-coordinate Al3+ ions andmore » the amount of strongly adsorbed ethanol molecules (i.e., the ones that convert to ethylene during TPD) is obtained. This result indicates that the penta-coordinate aluminum sites are the catalytic active sites on alumina surfaces during ethanol dehydration reaction across the entire course of gamma- to alpha-Al2O3 phase transformations.« less

Charge transfer photodissociation of phenol on Ag(111)

NASA Astrophysics Data System (ADS)

Lee, Junseok; Ryu, Sunmin; Ku, Jong Seok; Kim, Seong Keun

2001-12-01

The photochemistry of phenol on Ag(111) has been investigated by post-irradiation temperature programmed desorption (TPD). Ultraviolet (UV) irradiation at 355 and 266 nm was found to affect only the chemisorption layer in direct contact with the metal surface, while leaving the multilayer virtually intact. The main photoinduced reaction was found to be photodissociation of the O-H bond of phenol. Two new peaks were observed at the mass of phenol in the post-irradiation TPD spectrum at 335 K and 455 K. These peaks were assigned to the recombinative desorption of phenoxy with the hydrogen from O-H bond photodissociation and from thermal C-H bond fission, respectively. The photodissociation cross section was measured at different wavelengths and coverages. A charge transfer type photodissociation mechanism was proposed, where hot electrons generated in the substrate by UV photons attach to the affinity level of the adsorbed phenol. The transition to the transient anionic potential then leads to facile dissociation of O-H bond. The affinity level of phenol has been estimated to lie at 3.2-3.5 eV above the Fermi level for the 1 ML case.

Application of FIGAERO (Filter Inlet for Gases and AEROsol) coupled to a high resolution time of flight chemical ionization mass spectrometer to field and chamber organic aerosol: Implications for carboxylic acid formation and gas-particle partitioning from monoterpene oxidation

NASA Astrophysics Data System (ADS)

Lopez-Hilfiker, F.; Mohr, C.; Ehn, M.; Rubach, F.; Mentel, T. F.; Kleist, E.; Wildt, J.; Thornton, J. A.

2013-12-01

We present measurements of a large suite of gas and particle phase carboxylic acid containing compounds made with a Filter Inlet for Gas and AEROsol (FIGAERO) coupled to a high resolution time of flight chemical ionization mass spectrometer (HR-ToF-CIMS) developed at the University of Washington. A prototype operated with acetate negative ion proton transfer chemistry was deployed on the Julich Plant Atmosphere Chamber to study a-pinene oxidation, and a modified version was deployed at the SMEAR II forest station in Hyytiälä, Finland and SOAS, in Brent Alabama. We focus here on results from JPAC and Hyytiälä, where we utilized the same ionization method most selective towards carboxylic acids. In all locations, 100's of organic acid compounds were observed in the gas and particles and many of the same composition acids detected in the gas-phase were detected in the particles upon temperature programmed thermal desorption. Particulate organics detected by FIGAERO are highly correlated with organic aerosol mass measured by an AMS, providing additional volatility and molecular level information about collected aerosol. The fraction of a given compound measured in the particle phase follows expected trends with elemental composition, but many compounds would not be well described by an absorptive partitioning model assuming unity activity coefficients. Moreover the detailed structure in the thermal desorption signals reveals a contribution from thermal decomposition of large molecular weight organics and or oligomers with implications for partitioning measurements and model validation

Contribution of thermal energy to initial ion production in matrix-assisted laser desorption/ionization observed with 2,4,6-trihydroxyacetophenone.

PubMed

Lai, Yin-Hung; Chen, Bo-Gaun; Lee, Yuan Tseh; Wang, Yi-Sheng; Lin, Sheng Hsien

2014-08-15

Although several reaction models have been proposed in the literature to explain matrix-assisted laser desorption/ionization (MALDI), further study is still necessary to explore the important ionization pathways that occur under the high-temperature environment of MALDI. 2,4,6-Trihydroxyacetophenone (THAP) is an ideal compound for evaluating the contribution of thermal energy to an initial reaction with minimum side reactions. Desorbed neutral THAP and ions were measured using a crossed-molecular beam machine and commercial MALDI-TOF instrument, respectively. A quantitative model incorporating an Arrhenius-type desorption rate derived from transition state theory was proposed. Reaction enthalpy was calculated using GAUSSIAN 03 software with dielectric effect. Additional evidence of thermal-induced proton disproportionation was given by the indirect ionization of THAP embedded in excess fullerene molecules excited by a 450 nm laser. The quantitative model predicted that proton disproportionation of THAP would be achieved by thermal energy converted from a commonly used single UV laser photon. The dielectric effect reduced the reaction Gibbs free energy considerably even when the dielectric constant was reduced under high-temperature MALDI conditions. With minimum fitting parameters, observations of pure THAP and THAP mixed with fullerene both agreed with predictions. Proton disproportionation of solid THAP was energetically favorable with a single UV laser photon. The quantitative model revealed an important initial ionization pathway induced by the abrupt heating of matrix crystals. In the matrix crystals, the dielectric effect reduced reaction Gibbs free energy under typical MALDI conditions. The result suggested that thermal energy plays an important role in the initial ionization reaction of THAP. Copyright © 2014 John Wiley & Sons, Ltd.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ohashi, Haruhiko, E-mail: hohashi@spring8.or.jp; Senba, Yasunori; Yumoto, Hirokatsu

We studied typical forms of contamination on X-ray mirrors that cause degradation of beam quality, investigated techniques to remove the contaminants, and propose methods to eliminate the sources of the contamination. The total amount of carbon-containing substances on various materials in the vicinity of a mirror was measured by thermal desorption-gas chromatography/mass spectrometry and thermal desorption spectroscopy. It was found that cleanliness and ultra-high vacuum techniques are required to produce the contamination-free surfaces that are essential for the propagation of high-quality X-ray beams. The reduction of carbonaceous residue adsorbed on the surfaces, and absorbed into the bulk, of the materialsmore » in the vicinity of the mirrors is a key step toward achieving contamination-free X-ray optics.« less

Comparison of Ti-Based Coatings on Silicon Nanowires for Phosphopeptide Enrichment and Their Laser Assisted Desorption/Ionization Mass Spectrometry Detection

PubMed Central

Kurylo, Ievgen; Hamdi, Abderrahmane; Addad, Ahmed; Coffinier, Yannick

2017-01-01

We created different TiO2-based coatings on silicon nanowires (SiNWs) by using either thermal metallization or atomic layer deposition (ALD). The fabricated surfaces were characterized by X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDX), and reflectivity measurements. Surfaces with different TiO2 based coating thicknesses were then used for phosphopeptide enrichment and subsequent detection by laser desorption/ionization mass spectrometry (LDI-MS). Results showed that the best enrichment and LDI-MS detection were obtained using the silicon nanowires covered with 10 nm of oxidized Ti deposited by means of thermal evaporation. This sample was also able to perform phosphopeptide enrichment and MS detection from serum. PMID:28914806

Effect of surface polishing and vacuum firing on electron stimulated desorption from 316LN stainless steel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Malyshev, Oleg B., E-mail: oleg.malyshev@stfc.ac.uk; Hogan, Benjamin T.; Pendleton, Mark

2014-09-01

The reduction of thermal outgassing from stainless steel by surface polishing or vacuum firing is well-known in vacuum technology, and the consequent use of both techniques allows an even further reduction of outgassing. The aim of this study was to identify the effectiveness of surface polishing and vacuum firing for reducing electron-stimulated desorption (ESD) from 316LN stainless steel, which is a frequently used material for particle accelerator vacuum chambers and components. It was found that, unlike for thermal outgassing, surface polishing does not reduce the ESD yield and may even increase it, while vacuum firing of nonpolished sample reduces onlymore » the H{sub 2} ESD yield by a factor 2.« less

In situ ionic liquid dispersive liquid-liquid microextraction coupled to gas chromatography-mass spectrometry for the determination of organophosphorus pesticides.

PubMed

Cacho, J I; Campillo, N; Viñas, P; Hernández-Córdoba, M

2018-07-20

Nine organophosphorus pesticides (OPPs) were determined in environmental waters from different origins using in situ ionic liquid dispersive liquid microextraction (IL-DLLME). This preconcentration technique was coupled to gas chromatography-mass spectrometry (GC-MS) using microvial insert thermal desorption, an approach that uses a thermal desorption injector as sample introduction system. The parameters affecting both the microextraction and sample injection steps were optimized. The proposed method showed good precision, with RSD values ranging from 4.1 to 9.7%, accuracy with recoveries in the 85-118% range, and sensitivity with DLs ranging from 5 to 16 ng L -1 . Copyright © 2017 Elsevier B.V. All rights reserved.

Analysis of waterborne paints by gas chromatography-mass spectrometry with a temperature-programmable pyrolyzer.

PubMed

Nakamura, S; Takino, M; Daishima, S

2001-04-06

Gas chromatography-mass spectrometry (GC-MS) with a temperature-programmable pyrolyzer was used for the analysis of waterborne paints. Evolved gas analysis (EGA) profiles of the waterborne paints were obtained by this temperature-programmed pyrolysis directly coupled with MS via a deactivated metal capillary tube. The EGA profile suggested the optimal thermal desorption conditions for solvents and additives and the subsequent optimal pyrolysis temperature for the remaining polymeric material. Polymers were identified from pyrograms with the assistance of a new polymer library. The solvents were identified from the electron ionization mass spectra with the corresponding chemical ionization mass spectra. The additive was identified as zinc pyrithione by comparison with authentic standard. Zinc pyrithione cannot be analyzed by GC-MS as it is. However, the thermal decomposition products of zinc pyrithione could be detected. The information on the decomposition temperature and products was useful for the identification of the original compound.

Phase partitioning and volatility of secondary organic aerosol components formed from α-pinene ozonolysis and OH oxidation: the importance of accretion products and other low volatility compounds

DOE PAGES

Lopez-Hilfiker, F. D.; Mohr, C.; Ehn, M.; ...

2015-07-16

We measured a large suite of gas- and particle-phase multi-functional organic compounds with a Filter Inlet for Gases and AEROsols (FIGAERO) coupled to a high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) developed at the University of Washington. The instrument was deployed on environmental simulation chambers to study monoterpene oxidation as a secondary organic aerosol (SOA) source. We focus here on results from experiments utilizing an ionization method most selective towards acids (acetate negative ion proton transfer), but our conclusions are based on more general physical and chemical properties of the SOA. Hundreds of compounds were observed in both gas andmore » particle phases, the latter being detected by temperature-programmed thermal desorption of collected particles. Particulate organic compounds detected by the FIGAERO–HR-ToF-CIMS are highly correlated with, and explain at least 25–50 % of, the organic aerosol mass measured by an Aerodyne aerosol mass spectrometer (AMS). Reproducible multi-modal structures in the thermograms for individual compounds of a given elemental composition reveal a significant SOA mass contribution from high molecular weight organics and/or oligomers (i.e., multi-phase accretion reaction products). Approximately 50 % of the HR-ToF-CIMS particle-phase mass is associated with compounds having effective vapor pressures 4 or more orders of magnitude lower than commonly measured monoterpene oxidation products. The relative importance of these accretion-type and other extremely low volatility products appears to vary with photochemical conditions. We present a desorption-temperature-based framework for apportionment of thermogram signals into volatility bins. The volatility-based apportionment greatly improves agreement between measured and modeled gas-particle partitioning for select major and minor components of the SOA, consistent with thermal decomposition during desorption causing the conversion of lower volatility components into the detected higher volatility compounds.« less

Phase partitioning and volatility of secondary organic aerosol components formed from α-pinene ozonolysis and OH oxidation: the importance of accretion products and other low volatility compounds

DOE PAGES

Lopez-Hilfiker, F. D.; Mohr, C.; Ehn, M.; ...

2015-02-18

We measured a large suite of gas and particle phase multi-functional organic compounds with a Filter Inlet for Gases and AEROsols (FIGAERO) coupled to a high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) developed at the University of Washington. The instrument was deployed on environmental simulation chambers to study monoterpene oxidation as a secondary organic aerosol (SOA) source. We focus here on results from experiments utilizing an ionization method most selective towards acids (acetate negative ion proton transfer), but our conclusions are based on more general physical and chemical properties of the SOA. Hundreds of compounds were observed in both gasmore » and particle phases, the latter being detected upon temperature programmed thermal desorption of collected particles. Particulate organic compounds detected by the FIGAERO HR-ToF-CIMS are highly correlated with, and explain at least 25–50% of, the organic aerosol mass measured by an Aerodyne Aerosol Mass Spectrometer (AMS). Reproducible multi-modal structures in the thermograms for individual compounds of a given elemental composition reveal a significant SOA mass contribution from large molecular weight organics and/or oligomers (i.e. multi-phase accretion reaction products). Approximately 50% of the HR-ToF-CIMS particle phase mass is associated with compounds having effective vapor pressures 4 or more orders of magnitude lower than commonly measured monoterpene oxidation products. The relative importance of these accretion-type and other extremely low volatility products appears to vary with photochemical conditions. We present a desorption temperature based framework for apportionment of thermogram signals into volatility bins. The volatility-based apportionment greatly improves agreement between measured and modeled gas–particle partitioning for select major and minor components of the SOA, consistent with thermal decomposition during desorption causing the conversion of lower volatility components into the detected higher volatility compounds.« less

Structure and reaction properties of thin Al films deposited on Ni(110)

NASA Astrophysics Data System (ADS)

Hahn, Peter; Bertino, Massimo F.; Toennies, J. Peter; Ritter, Michael; Weiss, Werner

1998-09-01

A variety of experimental techniques, including scanning tunneling microscopy (STM) and thermal desorption spectroscopy (TDS) have been used to investigate the structure and reaction properties of thin Al films on Ni(110) as a model for technical Raney nickel catalysts. The measurements show that Al grows by the Volmer-Weber growth mode, with Al islands reaching a height of 30 Å before the first Al layer is completed. On exposure to deuterium the TDS spectra indicate that the addition of Al produces a new deuterium chemisorption state with a desorption energy which decreases from 27 to 14 kJ/mol with increasing deuterium coverage. This new bound state is attributed to deuterium atoms bound to adsorption sites in the vicinity of Al islands. Thermal desorption measurements also reveal that the deuterium initial sticking coefficient S0 decreases with Al coverage. The results can be explained by a simple model which shows that for low Al coverages each Al island inhibits deuterium dissociation in a region which is about three times larger than the island area.

Desorption Kinetics of Benzene and Cyclohexane from a Graphene Surface.

PubMed

Smith, R Scott; Kay, Bruce D

2018-01-18

The desorption kinetics for benzene and cyclohexane from a graphene covered Pt(111) surface were investigated using temperature-programmed desorption (TPD). The benzene desorption spectra show well-resolved monolayer and multilayer desorption peaks. The benzene monolayer and submonolayer TPD spectra for coverages greater than ∼0.1 ML have nearly the same desorption peak temperature and have line shapes which are consistent with first-order desorption kinetics. For benzene coverages greater than 1 ML, the TPD spectra align on a common leading edge which is consistent with zero-order desorption. An "inversion" procedure in which the prefactor is varied to find the value that best reproduces the entire set of experimental desorption spectra was used to analyze the benzene data. The inversion analysis of the benzene TPD spectra yielded a desorption activation energy of 54 ± 3 kJ/mol with a prefactor of 10 17±1 s -1 . The TPD spectra for cyclohexane also have well-resolved monolayer and multilayer desorption features. The desorption leading edges for the monolayer and the multilayer TPD spectra are aligned indicating zero-order desorption kinetics in both cases. An Arrhenius analysis of the monolayer cyclohexane TPD spectra yielded a desorption activation energy of 53.5 ± 2 kJ/mol with a prefactor of 10 16±1 ML s -1 .

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hanyu, Yuichiro, E-mail: y-hanyu@lucid.msl.titech.ac.jp; Domen, Kay; Nomura, Kenji

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

Desorption from interstellar grains

NASA Technical Reports Server (NTRS)

Leger, A.; Jura, M.; Omont, A.

1985-01-01

Different desorption mechanisms from interstellar grains are considered to resolve the conflict between the observed presence of gaseous species in molecular clouds and their expected depletion onto grains. The physics of desorption is discussed with particular reference to the process of grain heating and the specific heat of the dust material. Impulsive heating by X-rays and cosmic rays is addressed. Spot heating of the grains by cosmic rays and how this can lead to desorption of mantles from very large grains is considered. It is concluded that CO depletion on grains will be small in regions with A(V) less than five from the cloud surface and n(H) less than 10,000, in agreement with observations and in contrast to expectations from pure thermal equilibrium. Even in very dense and obscured regions and in the absence of internal ultraviolet sources, the classical evaporation of CO or N2 and O2-rich mantles by cosmic rays is important.

Adsorption and reaction of propene on Ni(100)

NASA Astrophysics Data System (ADS)

Kleyna, R.; Borgmann, D.; Wedler, G.

1998-05-01

Photoelectron spectroscopy (UPS, XPS) and thermal desorption techniques were used to study the chemisorption and decomposition reactions of propene on Ni(100). Propene is molecularly adsorbed at temperatures below 150 K. At saturation coverage the TD spectrum shows two propene desorption peaks at 155 and 225 K and three hydrogen desorption peaks at 300, 330 and 380 K with a shoulder at 420 K. No other desorbing species could be detected. The amount of desorption of propene was determined by XPS to be 20% of the saturation coverage. The electronic structure of adsorbed propene and the chemical nature of its decomposition products were deduced from UP and XP spectra taken at saturation coverage. Adsorption at low temperatures results in a π-bonded species which is stable up to 150 K. At temperatures above 150 K the UP spectra point to a σ-bonded species which decomposes further at temperatures above 260 K.

The Effect of Platinum-coatings on Hydrogen- and Water-absorption and Desorption Characteristics of Lithium Zirconate

NASA Astrophysics Data System (ADS)

Tsuchiya, B.; Bandow, S.; Nagata, S.; Saito, K.; Tokunaga, K.; Morita, K.

Hydrogen (H)- and water (H2O)-storage and desorption characteristics of 25 nm thick Pt films onLi2ZrO3composite materials, exposed to normal air at room temperature, have been investigated by means of elastic recoil detection (ERD), Rutherford backscattering spectrometry (RBS), weight gain measurement (WGM), and thermal desorption spectroscopy (TDS) techniques. It was found by the ERD and TDS that H and H2O were absorbed into the Pt-coated Li2ZrO3 in air at room temperature and desorbed from it in vacuum at much low temperatures of approximately 317 and 309 K, respectively. In addition, the WGM and TDS spectra revealed that the absorption and desorption characters ofsome gases such as CH4, CO, and CO2including H as well as H2Ointo the Li2ZrO3 bulk were improved by Pt deposition.

Seasonal Solar Thermal Absorption Energy Storage Development.

PubMed

Daguenet-Frick, Xavier; Gantenbein, Paul; Rommel, Mathias; Fumey, Benjamin; Weber, Robert; Gooneseker, Kanishka; Williamson, Tommy

2015-01-01

This article describes a thermochemical seasonal storage with emphasis on the development of a reaction zone for an absorption/desorption unit. The heat and mass exchanges are modelled and the design of a suitable reaction zone is explained. A tube bundle concept is retained for the heat and mass exchangers and the units are manufactured and commissioned. Furthermore, experimental results of both absorption and desorption processes are presented and the exchanged power is compared to the results of the simulations.

Effect of thermal stability on protein adsorption to silica using homologous aldo-keto reductases

PubMed Central

Felsovalyi, Flora; Patel, Tushar; Mangiagalli, Paolo; Kumar, Sanat K; Banta, Scott

2012-01-01

Gaining more insight into the mechanisms governing the behavior of proteins at solid/liquid interfaces is particularly relevant in the interaction of high-value biologics with storage and delivery device surfaces, where adsorption-induced conformational changes may dramatically affect biocompatibility. The impact of structural stability on interfacial behavior has been previously investigated by engineering nonwild-type stability mutants. Potential shortcomings of such approaches include only modest changes in thermostability, and the introduction of changes in the topology of the proteins when disulfide bonds are incorporated. Here we employ two members of the aldo-keto reductase superfamily (alcohol dehydrogenase, AdhD and human aldose reductase, hAR) to gain a new perspective on the role of naturally occurring thermostability on adsorbed protein arrangement and its subsequent impact on desorption. Unexpectedly, we find that during initial adsorption events, both proteins have similar affinity to the substrate and undergo nearly identical levels of structural perturbation. Interesting differences between AdhD and hAR occur during desorption and both proteins exhibit some level of activity loss and irreversible conformational change upon desorption. Although such surface-induced denaturation is expected for the less stable hAR, it is remarkable that the extremely thermostable AdhD is similarly affected by adsorption-induced events. These results question the role of thermal stability as a predictor of protein adsorption/desorption behavior. PMID:22619179

Effect of thermal stability on protein adsorption to silica using homologous aldo-keto reductases.

PubMed

Felsovalyi, Flora; Patel, Tushar; Mangiagalli, Paolo; Kumar, Sanat K; Banta, Scott

2012-08-01

Gaining more insight into the mechanisms governing the behavior of proteins at solid/liquid interfaces is particularly relevant in the interaction of high-value biologics with storage and delivery device surfaces, where adsorption-induced conformational changes may dramatically affect biocompatibility. The impact of structural stability on interfacial behavior has been previously investigated by engineering nonwild-type stability mutants. Potential shortcomings of such approaches include only modest changes in thermostability, and the introduction of changes in the topology of the proteins when disulfide bonds are incorporated. Here we employ two members of the aldo-keto reductase superfamily (alcohol dehydrogenase, AdhD and human aldose reductase, hAR) to gain a new perspective on the role of naturally occurring thermostability on adsorbed protein arrangement and its subsequent impact on desorption. Unexpectedly, we find that during initial adsorption events, both proteins have similar affinity to the substrate and undergo nearly identical levels of structural perturbation. Interesting differences between AdhD and hAR occur during desorption and both proteins exhibit some level of activity loss and irreversible conformational change upon desorption. Although such surface-induced denaturation is expected for the less stable hAR, it is remarkable that the extremely thermostable AdhD is similarly affected by adsorption-induced events. These results question the role of thermal stability as a predictor of protein adsorption/desorption behavior. Copyright © 2012 The Protein Society.

A technique for thermal desorption analyses suitable for thermally-labile, volatile compounds

USDA-ARS?s Scientific Manuscript database

Our group has for some time studied below ground plant produced volatile signals affecting nematode and insect behavior. The research requires repeated sampling of intact plant/soil systems in the lab as well as the field with the help of probes to minimize unwanted effects on the systems we are stu...

Irradiation effect on deuterium behaviour in low-dose HFIR neutron-irradiated tungsten

DOE PAGES

Shimada, Masashi; Cao, G.; Otsuka, T.; ...

2014-12-01

Tungsten samples were irradiated by neutrons in the High Flux Isotope Reactor, Oak Ridge National Laboratory at reactor coolant temperatures of 50-70°C to low displacement damage of 0.025 and 0.3 dpa under the framework of the US-Japan TITAN program (2007-2013). After cooling down, the HFIR neutron-irradiated tungsten samples were exposed to deuterium plasmas in the Tritium Plasma Experiment, Idaho National Laboratory at 100, 200 and 500 °C twice at the ion fluence of 5×10²⁵ m⁻² to reach a total ion fluence of 1×10²⁶ m⁻² in order to investigate the near surface deuterium retention and saturation via nuclear reaction analysis. Finalmore » thermal desorption spectroscopy was performed to elucidate irradiation effect on total deuterium retention. Nuclear reaction analysis results showed that the maximum near surface (<5 µm depth) deuterium concentration increased from 0.5 at % D/W in 0.025 dpa samples to 0.8 at. % D/W in 0.3 dpa samples. The large discrepancy between the total retention via thermal desorption spectroscopy and the near surface retention via nuclear reaction analysis indicated the deuterium was migrated and trapped in bulk (at least 50 µm depth for 0.025 dpa and 35 µm depth for 0.025 dpa) at 500 °C case even in the relatively low ion fluence of 10²⁶ m⁻².« less

A quantum chemical study of the decomposition of Keggin-structured heteropolyacids.

PubMed

Janik, Michael J; Bardin, Billy B; Davis, Robert J; Neurock, Matthew

2006-03-09

Heterpolyacids (HPAs) demonstrate catalytic activity for oxidative and acid-catalyzed hydrocarbon conversion processes. Deactivation and thermal instability, however, have prevented their widespread use. Herein, ab initio density functional theory is used to study the thermal decomposition of the Keggin molecular HPA structure through the desorption of constitutional water molecules. The overall reaction energy and activation barrier are computed for the overall reaction HnXM12O40-->Hn-2XM12O39+H2O. and subsequently used to predict the effect of HPA composition on thermal stability. For example, the desorption of a constitutional water molecule is found to be increasingly endothermic in the order silicomolybdic acid (H4SiMo12O40)

Fabrication of polyaniline-coated halloysite nanotubes by in situ chemical polymerization as a solid-phase microextraction coating for the analysis of volatile organic compounds in aqueous solutions.

PubMed

Abolghasemi, Mir Mahdi; Arsalani, Naser; Yousefi, Vahid; Arsalani, Mahmood; Piryaei, Marzieh

2016-03-01

We have synthesized an organic-inorganic polyaniline-halloysite nanotube composite by an in situ polymerization method. This nanocomposite is immobilized on a stainless-steel wire and can be used as a fiber coating for solid-phase microextraction. It was found that our new solid-phase microextraction fiber is an excellent adsorbent for the extraction of some volatile organic compounds in aqueous samples in combination with gas chromatography and mass spectrometry. The coating can be prepared easily, is mechanically stable, and exhibits relatively high thermal stability. It is capable of extracting phenolic compounds from water samples. Following thermal desorption, the phenols were quantified by gas chromatography with mass spectrometry. The effects of extraction temperature, extraction time, sample ionic strength, stirring rate, pH, desorption temperature and desorption time were studied. Under optimal conditions, the repeatability for one fiber (n = 5), expressed as the relative standard deviation, is between 6.2 and 9.1%. The detection limits range from 0.005 to 4 ng/mL. The method offers the advantage of being simple to use, with a shorter analysis time, lower cost of equipment and higher thermal stability of the fiber in comparison to conventional methods of analysis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Biological functioning of PAH-polluted and thermal desorption-treated soils assessed by fauna and microbial bioindicators.

PubMed

Cébron, Aurélie; Cortet, Jérôme; Criquet, Stéven; Biaz, Asmaa; Calvert, Virgile; Caupert, Cécile; Pernin, Céline; Leyval, Corinne

2011-11-01

A large number of soil bioindicators were used to assess biological diversity and activity in soil polluted with polycyclic aromatic hydrocarbons (PAHs) and the same soil after thermal desorption (TD) treatment. Abundance and biodiversity of bacteria, fungi, protozoa, nematodes and microarthropods, as well as functional parameters such as enzymatic activities and soil respiration, were assessed during a two year period of in situ monitoring. We investigated the influence of vegetation (spontaneous vegetation and Medicago sativa) and TD treatment on biological functioning. Multivariate analysis was performed to analyze the whole data set. A principal response curve (PRC) technique was used to evaluate the different treatments (various vegetation and contaminated vs. TD soil) contrasted with control (bare) soil over time. Our results indicated the value of using a number of complementary bioindicators, describing both diversity and functions, to assess the influence of vegetation on soil and discriminate polluted from thermal desorption (TD)-treated soil. Plants had an influence on the abundance and activity of all organisms examined in our study, favoring the whole trophic chain development. However, although TD-treated soil had a high abundance and diversity of microorganisms and fauna, enzymatic activities were weak because of the strong physical and chemical modifications of this soil. Copyright © 2011 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved.

Interaction of Ester-Functionalized Ionic Liquids with Atomically-Defined Cobalt Oxides Surfaces: Adsorption, Reaction and Thermal Stability.

PubMed

Xu, Tao; Waehler, Tobias; Vecchietti, Julia; Bonivardi, Adrian; Bauer, Tanja; Schwegler, Johannes; Schulz, Peter S; Wasserscheid, Peter; Libuda, Joerg

2017-12-06

Hybrid materials consisting of ionic liquid (ILs) films on supported oxides hold a great potential for applications in electronic and energy materials. In this work, we have performed surface science model studies scrutinizing the interaction of ester-functionalized ILs with atomically defined Co 3 O 4 (111) and CoO(100) surfaces. Both supports are prepared under ultra-high vacuum (UHV) conditions in form of thin films on Ir(100) single crystals. Subsequently, thin films of three ILs, 3-butyl-1-methyl imidazolium bis(trifluoromethyl-sulfonyl) imide ([BMIM][NTf 2 ]), 3-(4-methoxyl-4-oxobutyl)-1-methylimidazolium bis(trifluoromethyl-sulfonyl) imide ([MBMIM][NTf 2 ]), and 3-(4-isopropoxy-4-oxobutyl)-1-methylimidazolium bis(trifluoromethyl-sulfonyl) imide ([IPBMIM][NTf 2 ]), were deposited on these surfaces by physical vapor deposition (PVD). Time-resolved and temperature-programmed infrared reflection absorption spectroscopy (TR-IRAS, TP-IRAS) were applied to monitor in situ the adsorption, film growth, and thermally induced desorption. By TP-IRAS, we determined the multilayer desorption temperature of [BMIM][NTf 2 ] (360±5 K), [MBMIM][NTf 2 ] (380 K) and [IPBMIM][NTf 2 ] (380 K). Upon deposition below the multilayer desorption temperature, all three ILs physisorb on both cobalt oxide surfaces. However, strong orientation effects are observed in the first monolayer, where the [NTf 2 ] - ion interacts with the surface through the SO 2 groups and the CF 3 groups point towards the vacuum. For the two functionalized ILs, the [MBMIM] + and [IPBMIM] + interact with the surface Co 2+ ions of both surfaces via the CO group of their ester function. A very different behavior is found, if the ILs are deposited above the multilayer desorption temperature (400 K). While for [BMIM][NTf 2 ] and [MBMIM][NTf 2 ] a molecularly adsorbed monolayer film is formed, [IPBMIM][NTf 2 ] undergoes a chemical transformation on the CoO(100) surface. Here, the ester group is cleaved and the cation is chemically linked to the surface by formation of a surface carboxylate. The IL-derived species in the monolayer desorb at temperatures around 500 to 550 K. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A mass spectrometric system for analyzing thermal desorption spectra of ion-implanted argon and cesium in tungsten. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Wood, G. M., Jr.

1974-01-01

A mass spectrometric system for determining the characteristics of materials used in instrumental development and aerospace applications was developed. The desorption spectra of cesium that was ion-implanted into polycrystalline tungsten and the effects on the spectra of bombardment of the tungsten by low energy (70 eV) electrons were investigated. Work function changes were measured by the retarding potential diode method. Flash desorption characteristics were observed and gas-reaction mechanisms of the surface of heated metal filaments were studied. Desorption spectra were measured by linearly increasing the sample temperature at a selected rate, the temperature cycling being generated from a ramp-driven dc power supply, with the mass spectrometer tuned to a mass number of interest. Results of the study indicate an anomolous desorption mechanism following an electron bombardment of the sample surface. The enhanced spectra are a function of the post-bombardment time and energy and are suggestive of an increased concentration of cesium atoms, up to 10 or more angstroms below the surface.

Direct thermal desorption in the analysis of cheese volatiles by gas chromatography and gas chromatography-mass spectrometry: comparison with simultaneous distillation-extraction and dynamic headspace.

PubMed

Valero, E; Sanz, J; Martínez-Castro, I

2001-06-01

Direct thermal desorption (DTD) has been used as a technique for extracting volatile components of cheese as a preliminary step to their gas chromatographic (GC) analysis. In this study, it is applied to different cheese varieties: Camembert, blue, Chaumes, and La Serena. Volatiles are also extracted using other techniques such as simultaneous distillation-extraction and dynamic headspace. Separation and identification of the cheese components are carried out by GC-mass spectrometry. Approximately 100 compounds are detected in the examined cheeses. The described results show that DTD is fast, simple, and easy to automate; requires only a small amount of sample (approximately 50 mg); and affords quantitative information about the main groups of compounds present in cheeses.

Feasibility studies for the treatment and reuse of contaminated marine sediments.

PubMed

Bonomoa, L; Careghini, A; Dastoli, S; De Propris, L; Ferrari, G; Gabellini, M; Saponaro, S

2009-07-01

This paper presents preliminary results of laboratory tests aimed at evaluating the easibility of the remediation of marine sediments, which are polluted by mercury and petroleum hydrocarbons, dredged at the bay of Augusta (SR, Italy). The treatment is composed of two sequential steps: in the first, a cement-based granular material is produced (based on a high performance concrete approach); then, the volatile and the semi-volatile compounds in the granular material are removed by a thermal desorption step. Treated materials could be reused or put into caissons, according to their mechanical properties and environmental compatibility. The experiments were focused on evaluating the effect of the process parameter values on: (i) the evolution of cement hydration reactions, (ii) thermal desorption removal efficiencies, (iii) leaching behaviour of the treated material.

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

PubMed

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

2012-02-06

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

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

Shape-dependence of the thermal and photochemical reactions of methanol on nanocrystalline anatase TiO2

NASA Astrophysics Data System (ADS)

Bennett, David A.; Cargnello, Matteo; Diroll, Benjamin T.; Murray, Christopher B.; Vohs, John M.

2016-12-01

Structure-activity relationships and the influence of particle size and shape on the partial- and photo-oxidation of methanol on nanocrystalline anatase TiO2 were investigated using temperature-programmed desorption. The study employed two distinct nanoparticle morphologies: truncated bipyramids exposing primarily {101} facets, and flatter platelets exposing primarily {001} surfaces, whose nominal sizes ranged from 10 to 25 nm. The platelets were found to be more active for thermally-driven reactions, such as coupling of methoxide groups to produce dimethyl ether, and deoxygenation to produce methane. A dependence of the reactivity of {001} facets for the coupling of methoxide groups to produce dimethyl ether on facet size was also observed. In contrast to the thermally-driven reactions, the bipyramidal nanoparticles were observed to be more active for a range of photochemical reactions, including oxidation and coupling to produce methyl formate, and photo-decomposition of surface methoxide species. This study also shows how well-defined nanocrystals can be used to help bridge the materials gap between studies of single crystal model catalysts and their high surface area industrial analogs.

[Mass-spectrometric analysis of an anti-microbial preparation decamethoxine].

PubMed

Sukhodub, L F; Kosevich, M V; Shelkovskiĭ, V S; Volianskiĭ, Iu L

1989-11-01

I. I. Mechnikov Kharkov Research Institute of Microbiology, Vaccines and Sera, Ministry of Public Health of the Ukrainian SSR. The results of mass spectrometric investigation of decamethoxine++, an antimicrobial chemotherapeutic drug, are presented. It was shown that desorption-field mass spectrometry provided recording decamethoxine++ intensive quasimolecular ions [M.Cl]+ and [M]++ forming under conditions of high electric intensity only from the intact parent molecule. Hence, the presence of the peaks in the desorption field mass spectra made it possible to definitively determine decamethoxine++ in the samples. Therefore, the procedure of desorption-field mass spectrometry proved reliable in identification of bisquaternary ammonium compounds. Ways for thermal decomposition and mass spectrometric fragmentation of the decamethoxine++ molecule under various ionization conditions are also discussed.

Experimental and computational studies of positron-stimulated ion desorption from TiO2(1 1 0) surface

NASA Astrophysics Data System (ADS)

Yamashita, T.; Hagiwara, S.; Tachibana, T.; Watanabe, K.; Nagashima, Y.

2017-11-01

Experimental and computational studies of the positron-stimulated O+ ion desorption process from a TiO2(1 1 0) surface are reported. The measured data indicate that the O+ ion yields depend on the positron incident energy in the energy range between 0.5 keV and 15 keV. This dependence is closely related to the fraction of positrons which diffuse back to the surface after thermalization in the bulk. Based on the experimental and computational results, we conclude that the ion desorption via positron-stimulation occurs dominantly by the annihilation of surface-trapped positrons with core electrons of the topmost surface atoms.

NATURE OF UNRESOLVED COMPLEX MIXTURE IN SIZE-DISTRIBUTED EMISSIONS FROM RESIDENTIAL WOOD COMBUSTION AS MEASURED BY THERMAL DESORPTION-GAS CHROMATOGRAPHY-MASS SPECTROMETRY

EPA Science Inventory

In this study, the unresolved complex mixture (UCM) in size resolved fine aerosol emissions from residential wood combustion (RWC) is examined. The aerosols are sorted by size in an electrical low-pressure impactor (ELPI) and subsequently analyzed by thermal desorbtion/gas chroma...

Chemical surface modification of polycrystalline platinum thin-films to promote preferential chemisorption of n-hexane, piperidine, and cyclohexane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thomas, V.; Schwank, J.; Gland, J.

In this study, hard/soft Lewis acid-base (HSAB) principles are used to modify a thin-polycrystalline platinum film to promote preferential chemisorption of molecules such as piperidine, n-hexane, and cyclohexane. Specifically, the particle size and electron density distribution of the platinum surface is modified using thermal treatment and co-adsorption of electro-positive and negative species. These studies are conducted in an ultra-high vacuum chamber. The platinum surface is characterized, before and after modification protocols, using a variety of in-situ and ex-situ techniques. These include temperature programmed desorption (TPD), both resistance change and work function measurements, and both X-ray photoelectron spectroscopy and diffraction.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scherwitzl, Boris, E-mail: b.scherwitzl@tugraz.at; 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 ofmore » 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.« less

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

PubMed

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.

Nanoparticle assisted laser desorption/ionization mass spectrometry for small molecule analytes.

PubMed

Abdelhamid, Hani Nasser

2018-03-01

Nanoparticle assisted laser desorption/ionization mass spectrometry (NPs-ALDI-MS) shows remarkable characteristics and has a promising future in terms of real sample analysis. The incorporation of NPs can advance several methods including surface assisted LDI-MS, and surface enhanced LDI-MS. These methods have advanced the detection of many thermally labile and nonvolatile biomolecules. Nanoparticles circumvent the drawbacks of conventional organic matrices for the analysis of small molecules. In most cases, NPs offer a clear background without interfering peaks, absence of fragmentation of thermally labile molecules, and allow the ionization of species with weak noncovalent interactions. Furthermore, an enhancement in sensitivity and selectivity can be achieved. NPs enable straightforward analysis of target species in a complex sample. This review (with 239 refs.) covers the progress made in laser-based mass spectrometry in combination with the use of metallic NPs (such as AuNPs, AgNPs, PtNPs, and PdNPs), NPs consisting of oxides and chalcogenides, silicon-based NPs, carbon-based nanomaterials, quantum dots, and metal-organic frameworks. Graphical abstract An overview is given on nanomaterials for use in surface-assisted laser desorption/ionization mass spectrometry of small molecules.

Commercial silicon-on-insulator (SOI) wafers as a versatile substrate for laser desorption/ionization mass spectrometry.

PubMed

Kim, Shin Hye; Kim, Jeongkwon; Moon, Dae Won; Han, Sang Yun

2013-01-01

We report here that a commercial silicon-on-insulator (SOI) wafer offers an opportunity for laser desorption/ionization (LDI) of peptide molecules, which occurs directly from its flat surface without requiring special surface preparation. The LDI-on-SOI exhibits intact ionization of peptides with a good detection limit of lower than 20 fmol, of which the mass range is demonstrated up to insulin with citric acid additives. The LDI process most likely arises from laser-induced surface heating promoted by two-dimensional thermal confinement in the thin Si surface layer of the SOI wafer. As a consequence of the thermal process, the LDI-on-SOI method is also capable of creating post-source decay (PSD) of the resulting peptide LDI ions, which is suitable for peptide sequencing using conventional TOF/TOF mass spectrometry.

Surface cleaning and pure nitridation of GaSb by in-situ plasma processing

NASA Astrophysics Data System (ADS)

Gotow, Takahiro; Fujikawa, Sachie; Fujishiro, Hiroki I.; Ogura, Mutsuo; Chang, Wen Hsin; Yasuda, Tetsuji; Maeda, Tatsuro

2017-10-01

A clean and flat GaSb surface without native oxides has been attained by H2 plasma cleaning and subsequent in-situ N2 plasma nitridation process at 300 oC. The mechanisms of thermal desorption behavior of native oxides on GaSb have been studied by thermal desorption spectroscopy (TDS) analysis. The suitable heat treatment process window for preparing a clean GaSb surface is given. Auger electron spectroscopy (AES) analysis indicates that native oxides were completely removed on the GaSb surface after H2 plasma exposure and the pure nitridation of the clean GaSb surface was obtained at a relatively low temperature of 300 °C. This pure nitridation of GaSb have a possibility to be used as a passivation layer for high quality GaSb MOS devices.

Comparison of Adsorbed Mercury Screening Method With Cold-Vapor Atomic Absorption Spectrophotometry for Determination of Mercury in Soil

NASA Technical Reports Server (NTRS)

Easterling, Donald F.; Hovanitz, Edward S.; Street, Kenneth W.

2000-01-01

A field screening method for the determination of elemental mercury in environmental soil samples involves the thermal desorption of the mercury from the sample onto gold and then the thermal desorption from the gold to a gold-film mercury vapor analyzer. This field screening method contains a large number of conditions that could be optimized for the various types of soils encountered. In this study, the conditions were optimized for the determination of mercury in silty clay materials, and the results were comparable to the cold-vapor atomic absorption spectrophotometric method of determination. This paper discusses the benefits and disadvantages of employing the field screening method and provides the sequence of conditions that must be optimized to employ this method of determination on other soil types.

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

PubMed Central

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

2012-01-01

Different types of experimental studies are performed using the hydrogen storage alloy (HSA) MlNi3.6Co0.85Al0.3Mn0.3 (Ml: La-rich mischmetal), chemically surface treated, as the anode active material for application in a proton exchange membrane fuel cell (PEMFC). The recently developed molecular beam—thermal desorption spectrometry (MB-TDS) technique is here reported for detecting the electrochemical hydrogen uptake and release by the treated HSA. The MB-TDS allows an accurate determination of the hydrogen mass absorbed into the hydrogen storage alloy (HSA), and has significant advantages in comparison with the conventional TDS method. Experimental data has revealed that the membrane electrode assembly (MEA) using such chemically treated alloy presents an enhanced surface capability for hydrogen adsorption. PMID:28817043

Advanced structural analysis of nanoporous materials by thermal response measurements.

PubMed

Oschatz, Martin; Leistner, Matthias; Nickel, Winfried; Kaskel, Stefan

2015-04-07

Thermal response measurements based on optical adsorption calorimetry are presented as a versatile tool for the time-saving and profound characterization of the pore structure of porous carbon-based materials. This technique measures the time-resolved temperature change of an adsorbent during adsorption of a test gas. Six carbide and carbon materials with well-defined nanopore architecture including micro- and/or mesopores are characterized by thermal response measurements based on n-butane and carbon dioxide as the test gases. With this tool, the pore systems of the model materials can be clearly distinguished and accurately analyzed. The obtained calorimetric data are correlated with the adsorption/desorption isotherms of the materials. The pore structures can be estimated from a single experiment due to different adsorption enthalpies/temperature increases in micro- and mesopores. Adsorption/desorption cycling of n-butane at 298 K/1 bar with increasing desorption time allows to determine the pore structure of the materials in more detail due to different equilibration times. Adsorption of the organic test gas at selected relative pressures reveals specific contributions of particular pore systems to the increase of the temperature of the samples and different adsorption mechanisms. The use of carbon dioxide as the test gas at 298 K/1 bar provides detailed insights into the ultramicropore structure of the materials because under these conditions the adsorption of this test gas is very sensitive to the presence of pores smaller than 0.7 nm.

Analysis of a GC/MS thermal desorption system with simultaneous sniffing for determination of off-odor compounds and VOCs in fumes formed during extrusion coating of low-density polyethylene.

PubMed

Villberg, K; Veijanen, A

2001-03-01

A thermal desorption equipment introducing volatile organic compounds (VOCs) into the gas chromatographic/ mass spectrometric system (GC/MS) with simultaneous sniffing (SNIFF) is a suitable method for identifying the volatile organic off-odor compounds formed during the extrusion coating process of low-density polyethylene. Fumes emitted during the extrusion coating process of three different plastic materials were collected at two different temperatures (285 and 315 degrees C) from an outgoing pipe and near an extruder. The VOCs of fumes were analyzed by drawing a known volume of air through the adsorbent tube filled with a solid adsorbent (Tenax GR). The air samples were analyzed by using a special thermal desorption device and GC/MS determination. The simultaneous sniffing was carried out to detect off-odors and to assist in the identification of those compounds that contribute to tainting and smelling. The amounts of off-odor carbonyl compounds and the total content of the volatile organic compounds were determined. The most odorous compounds were identified as carboxylic acids while the majority of the volatile compounds were hydrocarbons. The detection and quantification of carboxylic acids were based on the characteristic ions of their mass spectra. The higher the extrusion temperature the more odors were detected. An important observation was that the total concentration of volatiles was dependent not only on the extrusion temperature but also on the plastic material.

Desorption of oxygen from alloyed Ag/Pt(111)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jankowski, Maciej; Wormeester, Herbert, E-mail: h.wormeester@utwente.nl; Zandvliet, Harold J. W.

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})more » 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.« less

Non-thermal Processes in the Formation of Mercury's Tenuous Exosphere

NASA Astrophysics Data System (ADS)

Schaible, M. J.; Bennett, C.; Jones, B. M.; Orlando, T. M.

2017-12-01

Recent observations from the MESSENGER spacecraft orbiting Mercury have established that a quasi-trapped population of ions and electrons with 1-10 keV energy exists at a distance of about 1.5 RM (RM is Mercury's radius) around much of the planet. Recent observations from the Fast Imaging Plasma Spectrometer (FIPS), taken < 400 km from the surface, have shown a plasma cusp with energetic heavy ions (i.e. Na+ and O+ groups). The sources of these ions are not clear. A newly developed global kinetic transport model suggests that electron-stimulated desorption (ESD), and possibly light ion stimulated desorption (ISD), can directly yield ions that can be transported and dynamically accelerated to the plasma cusp regions observed by FIPS. Neutrals desorbed from the surface by ESD, ISD, photon-stimulated desorption (PSD) and meteorite impact may also be photoionized and transported/injected into the cusp region. Though the relative importance of these mechanisms in the formation of Mercury's tenuous atmosphere and the subsequent effects on the exosphere/magnetosphere dynamics are not known, it is likely that all of these contribute significantly. The goals of this work are to measure desorption cross-sections and ejection velocities for Na+, O+, and water group ions under relevant electron and ion bombardment energies. This program utilizes state-of-the art surface science capabilities to probe the role of ESD and ISD as a source of ions and neutrals present in the exosphere of Mercury. The experimental chamber is equipped with a dosing system, a cryogenic cooled temperature controlled sample holder, as well as pulsed ion and electron sources. The ESD and ISD ion yields and velocity measurements are obtained directly by sampling with a time-of-flight mass spectrometer. The measured ESD ion yields from adsorbate covered Mercury surface analogs such as the sulfur bearing minerals MgS, Na2S and K2S are low. Additionally, ISD experiments using incident protons also yielded low ion signals. These results implicate PSD and neutral desorption as dominant processes. The information obtained from these experiments can be directly incorporated into model simulations for comparison with data recently obtained by the FIPS instrument.

Facile and Low-cost Synthesis of Mesoporous Ti-Mo Bi-metal Oxide Catalysts for Biodiesel Production from Esterification of Free Fatty Acids in Jatropha curcas Crude Oil.

PubMed

Zhang, Qiuyun; Li, Hu; Yang, Song

2018-05-01

Mesoporous Ti-Mo bi-metal oxides with various titanium-molybdenum ratios were successfully fabricated via a facile approach by using stearic acid as a low-cost template agent. thermal gravity (TG) /differential scanning calorimetry (DSC) analysis, X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, nitrogen adsorption-desorption isotherm, NH 3 temperature-programmed desorption (NH 3 -TPD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) measurements indicated these materials possessing mesoporous structure, sufficient pore size and high acid intensity. The catalytic performance of prepared catalysts was evaluated by esterification of free fatty acids in Jatropha curcas crude oil (JCCO) with methanol. The effects of various parameters on FFA conversion were investigated. The esterification conversion of 87.8% was achieved under the condition of 180°C, 2 h, methanol to JCCO molar ratio of 20:1 and 3.0 wt.% catalyst (relative to the weight of JCCO). The mesoporous catalysts were found to exhibit high activities toward the simultaneous esterification and transesterification of JCCO. Furthermore, the catalyst could be recovered with a good reusability.

Desorption dynamics of deuterium in CuCrZr alloy

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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)

Pulsed Laser Deposition of High Tc Superconducting Thin Films

DTIC Science & Technology

1992-04-15

Torr. This pressure is Mg capture by 02 decreases the desorption , in agreement high compared to pressures employed for the commonly with our...34’/C). Microplasticity ’F. 1. Grunthaner and P. J. Grunthaner, Mater. Sci. Rep 1. 65 (1986) has been observed 7 in Y’SZ at 23 *C, and may be involved...2.72 3.25 ing to Yadavalli er al.,15 thermal desorption of Mg is in- 300 S 162 1.97 2.40 3.10 hibited by lower substrate temperature and Mg oxidation

Ultrahigh Vacuum Studies of the Fundamental Interactions of Chemical Warfare Agents and Their Simulants with Amorphous Silica

DTIC Science & Technology

2015-07-14

Aldao, C. M. Monte Carlo Study of Thermal Desorption Curves of Water from Zeolite Type A. Langmuir 1996, 12, 36-39. (83) Gorte, R. J. Design Parameters...and Diffusion-Limited TPD of Water from Zeolite Linde 4A. Thermochimica Acta 1998, 319, 177-184. (85) Palmero, A.; Loffler, D. G. Kinetics of Water...Desorption from Pelletized 4A and 5A Zeolites . Thermochimica Acta 1990, 159, 171-176. (86) Dean, J. A. Lange’s Handbook of Chemistry; Fifteenth

Design and performance analysis of gas sorption compressors

NASA Technical Reports Server (NTRS)

Chan, C. K.

1984-01-01

Compressor kinetics based on gas adsorption and desorption processes by charcoal and for gas absorption and desorption processes by LaNi5 were analyzed using a two-phase model and a three-component model, respectively. The assumption of the modeling involved thermal and mechanical equilibria between phases or among the components. The analyses predicted performance well for compressors which have heaters located outside the adsorbent or the absorbent bed. For the rapidly-cycled compressor, where the heater was centrally located, only the transient pressure compared well with the experimental data.

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

PubMed

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

2015-06-08

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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermal desorption comprehensive two-dimensional gas chromatography coupled to time of flight mass spectrometry for vapour phase mainstream tobacco smoke analysis.

PubMed

Savareear, Benjamin; Brokl, Michał; Wright, Chris; Focant, Jean-Francois

2017-11-24

A thermal desorption comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (TD-GC×GC-TOFMS) method has been developed for the analysis of mainstream tobacco smoke (MTS) vapour phase (VP). The selection process of the sample introduction approach involved comparing the results obtained from three different approaches: a) use of gas sampling bag followed by SPME (Tedlar ® -SPME), b) gas sampling bag followed by TD (Tedlar ® -TD), and c) sampling directly on TD sorbents (Direct-TD). Six different SPME fibers and six different TD sorbent beds were evaluated for the extraction capacities in terms of total number of peaks and related intensities or peak areas. The best results were obtained for the Direct-TD approach using Tenax TA/Carbograph1TD/Carboxen1003 sorbent tubes. The optimisation of TD tube desorption parameters was carried out using a face-centered central composite experimental design and resulted in the use of the Tenax TA/Carbograph 1TD/Carboxen 1003 sorbent with a 7.5min desorption time, a 60mL/min tube desorption flow, and a 250°C tube desorption temperature. The optimised method was applied to the separation of MTS-VP constituents, with 665 analytes detected. The method precision ranged from 1% to 15% for over 99% of identified peak areas and from 0% to 3% and 0% to 1% for both first ( 1 t R ) and second ( 2 t R ) dimension retention times, respectively. The method was applied to the analyses of two cigarette types differing in their filter construction. Principal component analysis (PCA) allowed a clear differentiation of the studied cigarette types (PC1 describing 94% of the explained variance). Supervised Fisher ratio analysis permitted the identification of compounds responsible for the chemical differences between the two sample types. A set of 91 most relevant compounds was selected by applying a Fisher ratio cut-off approach and most of them were selectively removed by one of the cigarette filter types. Copyright © 2017 Elsevier B.V. All rights reserved.

Effectiveness of laser sources for contactless sampling of explosives

NASA Astrophysics Data System (ADS)

Akmalov, Artem E.; Chistyakov, Alexander A.; Kotkovskii, Gennadii E.

2016-05-01

A mass-spectrometric study of photo processes initiated by ultraviolet (UV) laser radiation in explosives adsorbed on metal and dielectric substrates has been performed. A calibrated quadrupole mass spectrometer was used to determine a value of activation energy of desorption and a quantity of explosives desorbed by laser radiation. A special vacuumoptical module was elaborated and integrated into a vacuum mass-spectrometric system to focus the laser beam on a sample. It has been shown that the action of nanosecond laser radiation set at q= 107 - 108 W/cm2, λ=266 nm on adsorbed layers of molecules of trinitrotoluene (TNT ) and pentaerytritoltetranitrate (PETN) leads not only to an effective desorption, but also to the non-equilibrium dissociation of molecules with the formation of nitrogen oxide NO. The cyclotrimethylenetrinitramine (RDX) dissociation products are observed only at high laser intensities (q> 109 W/cm2) thus indicating the thermal nature of dissociation, whereas desorption of RDX is observed even at q> 107 W/cm2 from all substrates. Desorption is not observed for cyclotetramethylenetetranitramine (HMX) under single pulse action: the dissociation products NO and NO2 are registered only, whereas irradiation at 10Hz is quite effective for HMX desorption. The results clearly demonstrate a high efficiency of nanosecond laser radiation with λ = 266 nm, q ~ 107 - 108 W/cm2, Epulse= 1mJ for desorption of molecules of explosives from various surfaces.

Interactions between glycine and amorphous solid water nanoscale films

NASA Astrophysics Data System (ADS)

Tzvetkov, George; Koller, Georg; Netzer, Falko P.

2012-12-01

The interactions of glycine (Gly) with amorphous solid water (ASW) nanolayers (≤ 100 ML), vapor-deposited on single crystalline AlOx surfaces at 100 K, have been investigated by near-edge X-ray absorption fine structure spectroscopy (NEXAFS) at the oxygen K-edge, temperature-programmed thermal desorption (TPD), X-ray photoelectron spectroscopy (XPS), and temperature-dependent work function measurements. Gly-on-ASW, ASW-on-Gly, and Gly on top of ASW-on-Gly ultrathin films have been fabricated. In contrast to the uniform ASW films grown directly on the hydrophilic AlOx, water molecules adsorb on the hydrophobic Gly films in the form of 3D ASW clusters. This leads to significant differences in the NEXAFS and work function data obtained from ASW-on-AlOx and ASW-on-Gly films, respectively. Furthermore, these structural differences influence the chemical state of Gly molecules (neutral vs. zwitterionic) adsorbed on top of ASW films. N1s XPS measurements revealed an increased amount of neutral Gly molecules in the film top-deposited on the ASW-on-Gly structure in comparison to the neutral Gly in the films directly condensed on AlOx or grown on the ASW substrate. H2O TPD spectra demonstrate that the crystallization and desorption processes of ASW are affected in a different way by the Gly layers, top-deposited on to ASW-on-AlOx and ASW-on-Gly films. At the same time, Gly adlayers sink into the ASW film during crystallization/desorption of the latter and land softly on the alumina surface in the form of zwitterionic clusters.

Electron-stimulated reactions in nanoscale water films adsorbed on α-Al 2O 3 (0001)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petrik, Nikolay G.; Kimmel, Gregory A.

The radiation-induced decomposition and desorption of nanoscale amorphous solid water (D2O) films adsorbed on -Al2O3(0001) surface was studied at low temperature in ultrahigh vacuum using temperature programmed desorption (TPD) and electron stimulated desorption (ESD) with a mono-energetic, low energy electron source. ESD yields of molecular products ( D2, O2 and D¬2O) and the total sputtering yield increased with increasing D2O coverage up to ~15 water monolayers (i.e. ~15 1015 cm-2) to a coverage-independent level for thicker water films. Experiments with isotopically-layered water films (D2O and H2O) demonstrated that the highest water decomposition yields occurred at the interfaces of the nanoscalemore » water films with the alumina substrate and vacuum. However, the increased reactivity of the water/alumina interface is relatively small compared to the enhancements in the non-thermal reactions previously observed at the water/Pt(111) and water/TiO2(110) interfaces. We propose that the relatively low activity of Al2O3(0001) for the radiation-induced production of molecular hydrogen is associated with lower reactivity of this surface with hydrogen atoms, which are likely precursors for the molecular hydrogen.100 eV electrons are stopped in the H 2O portion of the isotopically-layered nanoscale film on α-Al 2O 3(0001) but D 2is produced at the D 2O/alumina interface by mobile electronic excitations and/or hydronium ions.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ryota Ochiai; M. Azhar Uddin; Eiji Sasaoka

The effect of the presence of HCl and SO{sub 2} in the simulated coal combustion flue gas on the Hg{sup 0} removal by a commercial activated carbon (coconut shell AC) was investigated in a laboratory-scale fixed-bed reactor in a temperature range of 80-200{sup o}C. The characteristics (thermal stability) of the mercury species formed on the sorbents under various adsorption conditions were investigated by the temperature-programmed decomposition desorption (TPDD) technique. It was found that the presence of HCl and SO{sub 2} in the flue gas affected the mercury removal efficiency of the sorbents as well as the characteristics of the mercurymore » adsorption species. The mercury removal rate of AC increased with the HCl concentration in the flue gas. In the presence of HCl and the absence of SO{sub 2} during Hg{sup 0} adsorption by AC, a single Hg{sup 0} desorption peak at around 300{sup o}C was observed in the TPDD spectra and intensity of this peak increased with the HCl concentration during mercury adsorption. The peak at around 300{sup o}C may be derived from the decomposition and desorption of mercury chloride species. The presence of SO{sub 2} during mercury adsorption had an adverse effect on the mercury removal by AC in the presence of HCl. In the presence of both HCl and SO{sub 2} during Hg{sup 0} adsorption by AC, the major TPDD peak temperatures changed drastically depending upon the concentration of HCl and SO{sub 2} in flue gas during Hg{sup 0} adsorption. 16 refs., 7 figs.« less

Spontaneous desorption and phase transitions of self-assembled alkanethiol and alicyclic thiol monolayers chemisorbed on Au(111) in ultrahigh vacuum at room temperature.

PubMed

Ito, Eisuke; Kang, Hungu; Lee, Dongjin; Park, Joon B; Hara, Masahiko; Noh, Jaegeun

2013-03-15

Scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) were used to examine the surface structure and adsorption conditions of hexanethiol (HT) and cyclohexanethiol (CHT) self-assembled monolayers (SAMs) on Au(111) as a function of storage period in ultrahigh vacuum (UHV) conditions of 3×10(-7) Pa at room temperature (RT). STM imaging revealed that after storage for 7 days, HT SAMs underwent phase transitions from c(4×2) phase to low coverage 4×√3 phase. This transition is due to a structural rearrangement of hexanethiolates that results from the spontaneous desorption of chemisorbed HT molecules on Au(111) surface. XPS measurements showed approximately 28% reduction in sulfur coverage, which indicates desorption of hexanethiolates from the surfaces. Contrary to HT SAMs, the structural order of CHT SAMs with (5×2√3)R35° phase completely disappeared after storage for 3 or 7 days. XPS results show desorption of more than 80% of the cyclohexanethiolates, even after storage for 3 days. We found that spontaneous desorption of CHT molecules on Au(111) in UHV at RT occurred quickly, whereas spontaneous desorption of HT molecules was much slower. Thermal desorption spectroscopy (TDS) results suggest CHT SAMs in UHV at RT can desorb more efficiently than HT SAMs due to formation of thiol desorption fragments that result from chemical reactions between surface hydrogen atoms and thiolates on Au(111) surfaces. This study clearly demonstrated that organic thiols chemisorbed on gold surfaces are desorbed spontaneously in UHV at RT and van der Waals interactions play an important role in determining the structural stability of thiolate SAMs in UHV. Copyright © 2012 Elsevier Inc. All rights reserved.

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

Annual Quality Assurance Conference Files by Nicola Watson and Rui Li

EPA Pesticide Factsheets

26th Annual Quality Assurance Conference. Abstract: An Innovative Water Management Device for Online and Canister-based Thermal Desorption of Trace-level VVOCs in High Humidity Ambient Air by Nicola Watson and Rui Li

Ink dating using thermal desorption and gas chromatography/mass spectrometry: comparison of results obtained in two laboratories.

PubMed

Koenig, Agnès; Bügler, Jürgen; Kirsch, Dieter; Köhler, Fritz; Weyermann, Céline

2015-01-01

An ink dating method based on solvent analysis was recently developed using thermal desorption followed by gas chromatography/mass spectrometry (GC/MS) and is currently implemented in several forensic laboratories. The main aims of this work were to implement this method in a new laboratory to evaluate whether results were comparable at three levels: (i) validation criteria, (ii) aging curves, and (iii) results interpretation. While the results were indeed comparable in terms of validation, the method proved to be very sensitive to maintenances. Moreover, the aging curves were influenced by ink composition, as well as storage conditions (particularly when the samples were not stored in "normal" room conditions). Finally, as current interpretation models showed limitations, an alternative model based on slope calculation was proposed. However, in the future, a probabilistic approach may represent a better solution to deal with ink sample inhomogeneity. © 2014 American Academy of Forensic Science.

Effect of molecular desorption on the electronic properties of self-assembled polarizable molecular monolayers.

PubMed

Wang, Gunuk; Jeong, Hyunhak; Ku, Jamin; Na, Seok-In; Kang, Hungu; Ito, Eisuke; Jang, Yun Hee; Noh, Jaegeun; Lee, Takhee

2014-04-01

We investigated the interfacial electronic properties of self-assembled monolayers (SAM)-modified Au metal surface at elevated temperatures. We observed that the work functions of the Au metal surfaces modified with SAMs changed differently under elevated-temperature conditions based on the type of SAMs categorized by three different features based on chemical anchoring group, molecular backbone structure, and the direction of the dipole moment. The temperature-dependent work function of the SAM-modified Au metal could be explained in terms of the molecular binding energy and the thermal stability of the SAMs, which were investigated with thermal desorption spectroscopic measurements and were explained with molecular modeling. Our study will aid in understanding the electronic properties at the interface between SAMs and metals in organic electronic devices if an annealing treatment is applied. Copyright © 2013 Elsevier Inc. All rights reserved.

The fate or organic matter during planetary accretion - Preliminary studies of the organic chemistry of experimentally shocked Murchison meteorite

NASA Technical Reports Server (NTRS)

Tingle, Tracy N.; Tyburczy, James A.; Ahrens, Thomas J.; Becker, Christopher H.

1992-01-01

The fate of organic matter in carbonaceous meteorites during hypervelocity (1-2 km/sec) impacts is investigated using results of experiments in which three samples of the Murchison (CM2) carbonaceous chondrite were shocked to 19, 20, and 36 GPa and analyzed by highly sensitive thermal-desorption photoionization mass spectrometry (SALI). The thermal-desorptive SALI mass spectra of unshocked CM2 material revealed presence of indigenous aliphatic, aromatic, sulfur, and organosulfur compounds, and samples shocked to about 20 GPa showed little or no loss of organic matter. On the other hand, samples shocked to 36 GPa exhibited about 70 percent loss of organic material and a lower alkene/alkane ratio than did the starting material. The results suggest that it is unlikely that the indigenous organic matter in carbonaceous chondritelike planetesimals could have survived the impact on the earth in the later stages of earth's accretion.

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

Long-term fuel retention in JET ITER-like wall

NASA Astrophysics Data System (ADS)

Heinola, K.; Widdowson, A.; Likonen, J.; Alves, E.; Baron-Wiechec, A.; Barradas, N.; Brezinsek, S.; Catarino, N.; Coad, P.; Koivuranta, S.; Krat, S.; Matthews, G. F.; Mayer, M.; Petersson, P.; Contributors, JET

2016-02-01

Post-mortem studies with ion beam analysis, thermal desorption, and secondary ion mass spectrometry have been applied for investigating the long-term fuel retention in the JET ITER-like wall components. The retention takes place via implantation and co-deposition, and the highest retention values were found to correlate with the thickness of the deposited impurity layers. From the total amount of retained D fuel over half was detected in the divertor region. The majority of the retained D is on the top surface of the inner divertor, whereas the least retention was measured in the main chamber on the mid-plane of the inner wall limiter. The recessed areas of the inner wall showed significant contribution to the main chamber total retention. Thermal desorption spectroscopy analysis revealed the energetic T from DD reactions being implanted in the divertor. The total T inventory was assessed to be \\gt 0.3 {{mg}}.

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.

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.

Diffusion and Clustering of Carbon Dioxide on Non-porous Amorphous Solid Water

DOE Office of Scientific and Technical Information (OSTI.GOV)

He, Jiao; Emtiaz, Shahnewaj M.; Vidali, Gianfranco

2017-03-01

Observations by ISO and Spitzer toward young stellar objects showed that CO{sub 2} segregates in the icy mantles covering dust grains. Thermal processing of the ice mixture was proposed as being responsible for the segregation. Although several laboratories studied thermally induced segregation, a satisfying quantification is still missing. We propose that the diffusion of CO{sub 2} along pores inside water ice is the key to quantify segregation. We combined Temperature Programmed Desorption and Reflection Absorption InfraRed Spectroscopy to study how CO{sub 2} molecules interact on a non-porous amorphous solid water (np-ASW) surface. We found that CO{sub 2} diffuses significantly onmore » an np-ASW surface above 65 K and clusters are formed at well below one monolayer. A simple rate equation simulation finds that the diffusion energy barrier of CO{sub 2} on np-ASW is 2150 ± 50 K, assuming a diffusion pre-exponential factor of 10{sup 12} s{sup −1}. This energy should also apply to the diffusion of CO{sub 2} on the wall of pores. The binding energy of CO{sub 2} from CO{sub 2} clusters and CO{sub 2} from H{sub 2}O ice has been found to be 2415 ± 20 K and 2250 ± 20 K, respectively, assuming the same prefactor for desorption. CO{sub 2}–CO{sub 2} interaction is stronger than CO{sub 2}–H{sub 2}O interaction, in agreement with the experimental finding that CO{sub 2} does not wet the np-ASW surface. For comparison, we carried out similar experiments with CO on np-ASW, and found that the CO–CO interaction is always weaker than CO–H{sub 2}O. As a result, CO wets the np-ASW surface. This study should be of help to uncover the thermal history of CO{sub 2} on the icy mantles of dust grains.« less

Adsorption of laminaribiose in an in-situ product recovery process

NASA Astrophysics Data System (ADS)

Waluga, Thomas; Scholl, Stephan

2012-05-01

With the decreasing availability of fossil carbon sources new synthesis routes for pharmaceuticals and finechemicals find growing interest. Higher oligosaccharide laminaribiose can be produced by enzymatic synthesis from inexpensive sucrose. For an economic process an in-situ product removal by adsorption is investigated. BEA 50 zeolite shows high potential for application due to its good adsorption properties. Isotherms show Langmuir behavior and adequate loadings of nearly 100 mg ṡ g-1 can be reached. Other intermediates formed during the process do not adsorb on this zeolite or show weaker adsorption. Further thermal desorption can be used to regain laminaribiose. However the use of BEA 50 zeolite needs a sophisticated desorption process because of the zeolites' high acidity which catalyzes the degradation of laminaribiose. Hence lower temperatures have to be used or combined with displacement desorption.

Thermally annealed gold nanoparticles for surface-assisted laser desorption ionisation-mass spectrometry of low molecular weight analytes.

PubMed

Pilolli, Rosa; Ditaranto, Nicoletta; Di Franco, Cinzia; Palmisano, Francesco; Cioffi, Nicola

2012-10-01

Metal nanomaterials have an emerging role in surface-assisted laser desorption ionisation-mass spectrometry (SALDI-MS) providing a useful tool to overcome some limitations intrinsically related to the use of conventional organic matrices in matrix-assisted LDI-MS. In this contribution, the possibility to use a stainless-steel-supported gold nanoparticle (AuNP) film as a versatile platform for SALDI-MS was assessed. A sacrificial anode electrosynthetic route was chosen in order to obtain morphologically controlled core-shell AuNPs; the colloidal AuNPs were, thereafter, drop cast onto a stainless-steel sample plate and the resulting AuNP film was thermally annealed in order to improve its effectiveness as LDI-MS promoter. Spectroscopic characterization of the nanostructured film by X-ray photoelectron spectroscopy was crucial for understanding how annealing induced changes in the surface chemistry and influenced the performance of AuNPs as desorption/ionisation promoter. In particular, it was demonstrated that the post-deposition treatments were essential to enhance the AuNP core/analyte interaction, thus resulting in SALDI-MS spectra of significantly improved quality. The AuNP films were applied to the detection of three different classes of low molecular weight (LMW) analytes, i.e. amino acids, peptides and LMW polymers, in order to demonstrate the versatility of this nanostructured material.

Desorption of oxygen from YBa2Cu3O6+x films studied by Raman spectroscopy

NASA Astrophysics Data System (ADS)

Bock, A.; Kürsten, R.; Brühl, M.; Dieckmann, N.; Merkt, U.

1996-08-01

Phonons of laser-deposited YBa2Cu3O6+x films on MgO(100) substrates are investigated in a Raman setup as a function of laser power density. Investigations of YBa2Cu3O7 films allow us to study oxygen out-diffusion, where the onset of out-diffusion is indicated by the appearance of disorder-induced modes in the Raman spectra. At a pressure of 5×10-6 mbar the temperature threshold of the out-diffusion is (490+/-15) K. With increasing oxygen pressure the observed temperature thresholds rise only moderately in contrast to the behavior expected from the pox-T phase diagram of YBa2Cu3O6+x. Even at 1 bar oxygen partial pressure out-diffusion is observed and tetragonal sites with x=0 develop. These observations can be explained by photon-stimulated desorption of oxygen. Investigations of YBa2Cu3O6 films allow us to study oxygen in-diffusion. In 1 bar oxygen we observe competing oxygen fluxes due to thermally activated diffusion and photon-stimulated desorption. From these measurements we determine an upper bound of the thermal activation energy of the oxygen in-diffusion into YBa2Cu3O6 films of (0.19+/-0.01) eV.

A new technique to assess dermal absorption of volatile chemicals in vitro by thermal gravimetric analysis.

PubMed

Rauma, Matias; Isaksson, Tina S; Johanson, Gunnar

2006-10-01

Potential health hazards of dermal exposure, variability in reported dermal absorption rates and potential losses from the skin by evaporation indicate a need for a simple, inexpensive and standardized procedure to measure dermal absorption and desorption of chemical substances. The aim of this study was to explore the possibility to measure dermal absorption and desorption of volatile chemicals using a new gravimetric technique, namely thermal gravimetric analysis (TGA), and trypsinated stratum corneum from pig. Changes in skin weight were readily detected before, during and after exposure to vapours of water, 2-propanol, methanol and toluene. The shape and height of the weight curves differed between the four chemicals, reflecting differences in diffusivity and partial pressure and skin:air partitioning, respectively. As the skin weight is highly sensitive to the partial pressure of volatile chemicals, including water, this technique requires carefully controlled conditions with respect to air flow, temperature, chemical vapour generation and humidity. This new technique may help in the assessment of dermal uptake of volatile chemicals. Only a small piece of skin is needed and skin integrity is not necessary, facilitating the use of human samples. The high resolution weight-time curves obtained may also help to elucidate the characteristics of absorption, desorption and diffusion of chemicals in skin.

Gas chromatography with mass spectrometry for the determination of phthalates preconcentrated by microextraction based on an ionic liquid.

PubMed

Cacho, Juan Ignacio; Campillo, Natalia; Viñas, Pilar; Hernández-Córdoba, Manuel

2017-03-01

A new procedure is proposed for the analysis of migration test solutions obtained from plastic bottles used in the packaging of edible oils. Ultrasound-assisted emulsification microextraction with ionic liquids was applied for the preconcentration of six phthalate esters: dimethylphthalate, diethylphthalate, di-n-butylphthalate, n-butylbenzylphthalate, di-2-ethylhexylphthalate, and di-n-octylphthalate. The enriched ionic liquid was directly analyzed by gas chromatography and mass spectrometry using direct insert microvial thermal desorption. The different factors affecting the microextraction efficiency, such as volume of the extracting phase (30 μL of the ionic liquid) and ultrasound application time (25 s), and the thermal desorption step, such as desorption temperature and time, and gas flow rate, were studied. Under the selected conditions, detection limits for the analytes were in the 0.012-0.18 μg/L range, while recovery assays provided values ranging from 80 to 112%. The use of butyl benzoate as internal standard increased the reproducibility of the analytical procedure. When the release of the six phthalate esters from the tested plastic bottles to liquid simulants was monitored using the optimized procedure, analyte concentrations of between 1.0 and 273 μg/L were detected. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Factors Influencing NO2 Adsorption/Reduction on Microporous Activated Carbon: Porosity vs. Surface Chemistry

PubMed Central

Ghouma, Imen; Limousy, Lionel; Bennici, Simona

2018-01-01

The textural properties and surface chemistry of different activated carbons, prepared by the chemical activation of olive stones, have been investigated in order to gain insight on the NO2 adsorption mechanism. The parent chemical activated carbon was prepared by the impregnation of olive stones in phosphoric acid followed by thermal carbonization. Then, the textural properties and surface chemistry were modified by chemical treatments including nitric acid, sodium hydroxide and/or a thermal treatment at 900 °C. The main properties of the parent and modified activated carbons were analyzed by N2-adsorption, scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR) techniques, in order to enlighten the modifications issued from the chemical and thermal treatments. The NO2 adsorption capacities of the different activated carbons were measured in fixed bed experiments under 500 ppmv NO2 concentrations at room temperature. Temperature programmed desorption (TPD) was applied after adsorption tests in order to quantify the amount of the physisorbed and chemisorbed NO2. The obtained results showed that the development of microporosity, the presence of oxygen-free sites, and the presence of basic surface groups are key factors for the efficient adsorption of NO2. PMID:29670008

Thermal Stability of Goethite-Bound Natural Organic Matter Is Impacted by Carbon Loading.

PubMed

Feng, Wenting; Klaminder, Jonatan; Boily, Jean-François

2015-12-24

Dissolved natural organic matter (NOM) sorption at mineral surfaces can significantly affect the persistence of organic carbon in soils and sediments. Consequently, determining the mechanisms that stabilize sorbed NOM is crucial for predicting the persistence of carbon in nature. This study determined the effects of loadings and pH on the thermal stability of NOM associated with synthetic goethite (α-FeOOH) particle surfaces, as a proxy for NOM-mineral interactions taking place in nature. NOM thermal stability was investigated using temperature-programmed desorption (TPD) in the 30-700 °C range to collect vibration spectra of thermally decomposing goethite-NOM assemblages, and to concomitantly analyze evolved gases using mass spectrometry. Results showed that NOM thermal stability, indicated by the range of temperatures in which CO2 evolved during thermal decomposition, was greatest in unbound NOM and lowest when NOM was bound to goethite. NOM thermal stability was also loading dependent. It decreased when loadings were in increased the 0.01 to 0.42 mg C m(-2) range, where the upper value corresponds to a Langmuirian adsorption maximum. Concomitant Fourier transform infrared (FTIR) spectroscopy measurement showed that these lowered stabilities could be ascribed to direct NOM-goethite interactions that dominated the NOM binding environment. Mineral surface interactions at larger loadings involved, on the contrary, a smaller fraction of the sorbed NOM, thus increasing thermal stability toward that of its unbound counterpart. This study thus identifies a sorption threshold below which NOM sorption to goethite decreases NOM thermal stability, and above which no strong effects are manifested. This should likely influence the fate of organic carbon exposed to thermal gradients in natural environments.

Detection of gaseous compounds by needle trap sampling and direct thermal-desorption photoionization mass spectrometry: concept and demonstrative application to breath gas analysis.

PubMed

Kleeblatt, Juliane; Schubert, Jochen K; Zimmermann, Ralf

2015-02-03

A fast detection method to analyze gaseous organic compounds in complex gas mixtures was developed, using a needle trap device (NTD) in conjunction with thermal-desorption photoionization time-of-flight mass spectrometry (TD-PI-TOFMS). The mass spectrometer was coupled via a deactivated fused silica capillary to an injector of a gas chromatograph. In the hot injector, the analytes collected on the NTD were thermally desorbed and directly transferred to the PI-TOFMS ion source. The molecules are softly ionized either by single photon ionization (SPI, 118 nm) or by resonance enhanced multiphoton ionization (REMPI, 266 nm), and the molecular ion signals are detected in the TOF mass analyzer. Analyte desorption and the subsequent PI-TOFMS detection step only lasts ten seconds. The specific selectivity of REMPI (i.e., aromatic compounds) and universal ionization characteristics render PI-MS as a promising detection system. As a first demonstrative application, the alveolar phase breath gas of healthy, nonsmoking subjects was sampled on NTDs. While smaller organic compounds such as acetone, acetaldehyde, isoprene, or cysteamine can be detected in the breath gas with SPI, REMPI depicts the aromatic substances phenol and indole at 266 nm. In the breath gas of a healthy, smoking male subject, several xenobiotic substances such as benzene, toluene, styrene, and ethylbenzene can be found as well. Furthermore, the NTD-REMPI-TOFMS setup was tested for breath gas taken from a mechanically ventilated pig under continuous intravenous propofol (2,6-diisopropylphenol, narcotic drug) infusion.

Highly hydrogen-sensitive thermal desorption spectroscopy system for quantitative analysis of low hydrogen concentration (˜1 × 1016 atoms/cm3) in thin-film samples

NASA Astrophysics Data System (ADS)

Hanna, Taku; Hiramatsu, Hidenori; Sakaguchi, Isao; Hosono, Hideo

2017-05-01

We developed a highly hydrogen-sensitive thermal desorption spectroscopy (HHS-TDS) system to detect and quantitatively analyze low hydrogen concentrations in thin films. The system was connected to an in situ sample-transfer chamber system, manipulators, and an rf magnetron sputtering thin-film deposition chamber under an ultra-high-vacuum (UHV) atmosphere of ˜10-8 Pa. The following key requirements were proposed in developing the HHS-TDS: (i) a low hydrogen residual partial pressure, (ii) a low hydrogen exhaust velocity, and (iii) minimization of hydrogen thermal desorption except from the bulk region of the thin films. To satisfy these requirements, appropriate materials and components were selected, and the system was constructed to extract the maximum performance from each component. Consequently, ˜2000 times higher sensitivity to hydrogen than that of a commercially available UHV-TDS system was achieved using H+-implanted Si samples. Quantitative analysis of an amorphous oxide semiconductor InGaZnO4 thin film (1 cm × 1 cm × 1 μm thickness, hydrogen concentration of 4.5 × 1017 atoms/cm3) was demonstrated using the HHS-TDS system. This concentration level cannot be detected using UHV-TDS or secondary ion mass spectroscopy (SIMS) systems. The hydrogen detection limit of the HHS-TDS system was estimated to be ˜1 × 1016 atoms/cm3, which implies ˜2 orders of magnitude higher sensitivity than that of SIMS and resonance nuclear reaction systems (˜1018 atoms/cm3).

Diffusion Analysis Of Hydrogen-Desorption Measurements

NASA Technical Reports Server (NTRS)

Danford, Merlin D.

1988-01-01

Distribution of hydrogen in metal explains observed desorption rate. Report describes application of diffusion theory to anaylsis of experimental data on uptake and elimination of hydrogen in high-strength alloys of 25 degree C. Study part of program aimed at understanding embrittlement of metals by hydrogen. Two nickel-base alloys, Rene 41 and Waspaloy, and one ferrous alloy, 4340 steel, studied. Desorption of hydrogen explained by distribution of hydrogen in metal. "Fast" hydrogen apparently not due to formation of hydrides on and below surface as proposed.

GUIDE FOR CONDUCTING TREATABILITY STUDIES UNDER CERCLA: THERMAL DESORPTION - INTERIM GUIDANCE

EPA Science Inventory

Systematically conducted, well-documented treatability studies are an important component of the remedial investigation/feasibility study (RI/FS) process and the remedial design remedial action (RD/RA) process under the Comprehensive Environmental Response, Compensation, and Liab...

The DNAPL Remediation Challenge: Is There a Case for Source Depletion?

DTIC Science & Technology

2003-12-01

fermentation products acting as electron donors to promote reductive dechlorination of chlorinated solvents (e.g., see discussion on Sages and Bachman...has been primarily used to remove organic contamination in the vadose zone (see e.g., Stegemeier and Vinegar , 2001). Signifi cant removals of...Stegemeier, G.L., and H.J. Vinegar . 2001. Thermal conduction heating for in-situ thermal desorption of soils. In: Hazardous and Radioactive Waste Treatment

The use of nanomaterials for mass spectrometry can be uplifting for analyte detection

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, J.; Lipson, R. H.

2014-03-31

Surface-Assisted Laser Desorption Ionization (SALDI) involves desorbing and ionizing analyte molecules from a nanoporous substrate by laser irradiation for detection in a mass spectrometer. In this work experiments were designed to better understand the mechanisms governing desorption and ionization for Desorption Ionization On Silicon (DIOS), a variant of SALDI which uses porous silicon (pSi) as a substrate. Experiments are also reported for other nanoporous semiconducting materials (WO{sub 3}, TiO{sub 2}) which exhibit very similar behaviors; specifically, that both protonated analyte ions and analyte radical cations can be generated with relative intensities that depend on the position of the incident lasermore » focus relative to substrate surface. While thermal desorption appears to be important, preliminary evidence suggests that the ionization mechanism leading to protonated analytes involves in part electrons and holes formed when photoexciting the substrate above its electronic band gap, and the presence of defect states within the band gap. Radical cation formation appears to be driven in part by electron transfer due to the large electron affinity of each substrate used in this work.« less

Studies of solid carbon dioxide in interstellar ice analogs subject to thermal processing

NASA Astrophysics Data System (ADS)

White, Douglas W.

2010-09-01

Solid CO2 has been detected in many lines of sight in the interstellar medium from infrared observatories. Spectral profiles from space-based observatories have suggested that CO2 on icy grain mantles is mixed with other common molecules such as H2O and CH 3OH in interstellar regions and that thermal annealing has occurred. The vibrational mode at 658 cm-1 (15.2 mum) is suspected to be a powerful diagnostic tool as to the composition of species on icy grain mantles as well as thermal histories. However, previous studies have not systematically investigated ice composition and temperature. Laboratory spectra of interstellar ice analogs have been created in this study order to better understand the physical properties of solid CO2 in these interstellar environments. Existing databases of ice composition studies and effects of ice thermal history were updated in this study to include a more systematic approach. The 658 cm-1 (15.2 mum) bending mode feature of CO2 is examined here and the subsequent astrophysical implications stated. In the first set of experiments, 47 mixtures of H2O,CH3OH, andCO2 were slowly warmed and mid-infrared absorption spectra were recorded at 5K intervals. The second set of experiments involved examining the CO2 bending mode feature of 10 different CO2-containing ice mixtures at different temperatures where ice segregation was suspected. In these experiments, the ice mixtures were slowly heated to the desired temperature for increasing time intervals before cooling down and recording mid-IR absorption spectra. These studies may be used to analyze IR data from space-based observatories such as the Spitzer Space Telescope Infrared Spectrograph as well other future IR observations of the interstellar medium. Finally, mass spectroscopy measurements were taken from temperature programmed desorption (TPD) experiments performed on several binary mixtures of H2O + CO2 and CH 3OH + CO2. Physical properties such as desorption energy of CO2 can be determined from the TPD traces of these experiments. The work provided here addresses the physical properties of solid CO 2 thermally processed in ice mixtures in interstellar environments by laboratory simulations spectroscopically analyzed by mid-infrared absorption profiles and TPD.

Near-equilibrium desorption of helium films

NASA Astrophysics Data System (ADS)

Weimer, M.; Housley, R. M.; Goodstein, D. L.

1987-10-01

The thermal desorption of helium films in the presence of their equilibrium vapor is studied experimentally for small but rapid departures from ambient temperature. The results are analyzed within the framework of a quasithermodynamic phenomenological model based on detailed balance. Under the usual experimental conditions, isothermal desorption at the temperature of the substrate is a general prediction of the model which seems to be substantiated. For realistic adsorption isotherms the time evolution of the net desorption flux nevertheless appears to be governed by a highly nonlinear equation. In such circumstances, a number of characteristic relaxation times may be identified. These time scales are distinct from, and in general unrelated to, the coverage-dependent mean lifetime of an atom on the surface. To characterize the overall nonlinear evolution towards steady state, a global time scale, defined in terms of both initial- and steady-state properties, is introduced to summarize the experimental data. Internal evidence suggests a criterion for judging when collisions among desorbed atoms are unimportant. When this condition is satisfied, data for near-equilibrium desorption agree well with the predictions of the model. Combining our results with earlier data at higher substrate temperatures and different ambient conditions, the overall picture is consistent with scaling properties implied by the theory. We show that the values of the parameters deduced from a Frenkel-Arrhenius parametrization of the global relaxation times, as well as a variety of other aspects of desorption kinetics, are actually consequences of the shape of the equilibrium adsorption isotherm.

Ellipsometry-based combination of isothermal sorption-desorption measurement and temperature programmed desorption technique: A probe for interaction of thin polymer films with solvent vapor.

PubMed

Efremov, Mikhail Yu; Nealey, Paul F

2018-05-01

An environmental chamber equipped with an in situ spectroscopic ellipsometer, programmatic vapor pressure control, and variable temperature substrate holder has been designed for studying polymer coating behavior during an exposure to a solvent vapor and also for probing the residual solvent in the film afterwards. Both sorption-desorption cycle at a constant temperature and temperature programmed desorption (TPD) of the residual solvent manifest themselves as a change of the film thickness. Monitoring of ellipsometric angles of the coating allows us to determine the thickness as a function of the vapor pressure or sample temperature. The solvent vapor pressure is precisely regulated by a computer-controlled pneumatics. TPD spectra are recorded during heating of the film in an oil-free vacuum. The vapor pressure control system is described in detail. The system has been tested on 6-170 nm thick polystyrene, poly(methyl methacrylate), and poly(2-vinyl pyridine) films deposited on silicon substrates. Liquid toluene, water, ethanol, isopropanol, cyclohexane, 1,2-dichloroethane, and chlorobenzene were used to create a vapor atmosphere. Typical sorption-desorption and TPD curves are shown. The instrument achieves sub-monolayer sensitivity for adsorption studies on flat surfaces. Polymer-solvent vapor systems with strong interaction demonstrate characteristic absorption-desorption hysteresis spanning from vacuum to the glass transition pressure. Features on the TPD curves can be classified as either glass transition related film contraction or low temperature broad contraction peak. Typical absorption-desorption and TPD dependencies recorded for the 6 nm thick polystyrene film demonstrate the possibility to apply the presented technique for probing size effects in extremely thin coatings.

Ellipsometry-based combination of isothermal sorption-desorption measurement and temperature programmed desorption technique: A probe for interaction of thin polymer films with solvent vapor

NASA Astrophysics Data System (ADS)

Efremov, Mikhail Yu.; Nealey, Paul F.

2018-05-01

An environmental chamber equipped with an in situ spectroscopic ellipsometer, programmatic vapor pressure control, and variable temperature substrate holder has been designed for studying polymer coating behavior during an exposure to a solvent vapor and also for probing the residual solvent in the film afterwards. Both sorption-desorption cycle at a constant temperature and temperature programmed desorption (TPD) of the residual solvent manifest themselves as a change of the film thickness. Monitoring of ellipsometric angles of the coating allows us to determine the thickness as a function of the vapor pressure or sample temperature. The solvent vapor pressure is precisely regulated by a computer-controlled pneumatics. TPD spectra are recorded during heating of the film in an oil-free vacuum. The vapor pressure control system is described in detail. The system has been tested on 6-170 nm thick polystyrene, poly(methyl methacrylate), and poly(2-vinyl pyridine) films deposited on silicon substrates. Liquid toluene, water, ethanol, isopropanol, cyclohexane, 1,2-dichloroethane, and chlorobenzene were used to create a vapor atmosphere. Typical sorption-desorption and TPD curves are shown. The instrument achieves sub-monolayer sensitivity for adsorption studies on flat surfaces. Polymer-solvent vapor systems with strong interaction demonstrate characteristic absorption-desorption hysteresis spanning from vacuum to the glass transition pressure. Features on the TPD curves can be classified as either glass transition related film contraction or low temperature broad contraction peak. Typical absorption-desorption and TPD dependencies recorded for the 6 nm thick polystyrene film demonstrate the possibility to apply the presented technique for probing size effects in extremely thin coatings.

Large scale nanoparticle screening for small molecule analysis in laser desorption ionization mass spectrometry

DOE PAGES

Yagnik, Gargey B.; Hansen, Rebecca L.; Korte, Andrew R.; ...

2016-08-30

Nanoparticles (NPs) have been suggested as efficient matrixes for small molecule profiling and imaging by laser-desorption ionization mass spectrometry (LDI-MS), but so far there has been no systematic study comparing different NPs in the analysis of various classes of small molecules. Here, we present a large scale screening of 13 NPs for the analysis of two dozen small metabolite molecules. Many NPs showed much higher LDI efficiency than organic matrixes in positive mode and some NPs showed comparable efficiencies for selected analytes in negative mode. Our results suggest that a thermally driven desorption process is a key factor for metalmore » oxide NPs, but chemical interactions are also very important, especially for other NPs. Furthermore, the screening results provide a useful guideline for the selection of NPs in the LDI-MS analysis of small molecules.« less

Large scale nanoparticle screening for small molecule analysis in laser desorption ionization mass spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yagnik, Gargey B.; Hansen, Rebecca L.; Korte, Andrew R.

Nanoparticles (NPs) have been suggested as efficient matrixes for small molecule profiling and imaging by laser-desorption ionization mass spectrometry (LDI-MS), but so far there has been no systematic study comparing different NPs in the analysis of various classes of small molecules. Here, we present a large scale screening of 13 NPs for the analysis of two dozen small metabolite molecules. Many NPs showed much higher LDI efficiency than organic matrixes in positive mode and some NPs showed comparable efficiencies for selected analytes in negative mode. Our results suggest that a thermally driven desorption process is a key factor for metalmore » oxide NPs, but chemical interactions are also very important, especially for other NPs. Furthermore, the screening results provide a useful guideline for the selection of NPs in the LDI-MS analysis of small molecules.« less

Characterization of Adsorption Enthalpy of Novel Water-Stable Zeolites and Metal-Organic Frameworks

NASA Astrophysics Data System (ADS)

Kim, Hyunho; Cho, H. Jeremy; Narayanan, Shankar; Yang, Sungwoo; Furukawa, Hiroyasu; Schiffres, Scott; Li, Xiansen; Zhang, Yue-Biao; Jiang, Juncong; Yaghi, Omar M.; Wang, Evelyn N.

2016-01-01

Water adsorption is becoming increasingly important for many applications including thermal energy storage, desalination, and water harvesting. To develop such applications, it is essential to understand both adsorbent-adsorbate and adsorbate-adsorbate interactions, and also the energy required for adsorption/desorption processes of porous material-adsorbate systems, such as zeolites and metal-organic frameworks (MOFs). In this study, we present a technique to characterize the enthalpy of adsorption/desorption of zeolites and MOF-801 with water as an adsorbate by conducting desorption experiments with conventional differential scanning calorimetry (DSC) and thermogravimetric analyzer (TGA). With this method, the enthalpies of adsorption of previously uncharacterized adsorbents were estimated as a function of both uptake and temperature. Our characterizations indicate that the adsorption enthalpies of type I zeolites can increase to greater than twice the latent heat whereas adsorption enthalpies of MOF-801 are nearly constant for a wide range of vapor uptakes.

Characterization of Adsorption Enthalpy of Novel Water-Stable Zeolites and Metal-Organic Frameworks

PubMed Central

Kim, Hyunho; Cho, H. Jeremy; Narayanan, Shankar; Yang, Sungwoo; Furukawa, Hiroyasu; Schiffres, Scott; Li, Xiansen; Zhang, Yue-Biao; Jiang, Juncong; Yaghi, Omar M.; Wang, Evelyn N.

2016-01-01

Water adsorption is becoming increasingly important for many applications including thermal energy storage, desalination, and water harvesting. To develop such applications, it is essential to understand both adsorbent-adsorbate and adsorbate-adsorbate interactions, and also the energy required for adsorption/desorption processes of porous material-adsorbate systems, such as zeolites and metal-organic frameworks (MOFs). In this study, we present a technique to characterize the enthalpy of adsorption/desorption of zeolites and MOF-801 with water as an adsorbate by conducting desorption experiments with conventional differential scanning calorimetry (DSC) and thermogravimetric analyzer (TGA). With this method, the enthalpies of adsorption of previously uncharacterized adsorbents were estimated as a function of both uptake and temperature. Our characterizations indicate that the adsorption enthalpies of type I zeolites can increase to greater than twice the latent heat whereas adsorption enthalpies of MOF-801 are nearly constant for a wide range of vapor uptakes. PMID:26796523

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.

Laser-Induced Acoustic Desorption/Electron Ionization of Amino Acids and Small Peptides

NASA Astrophysics Data System (ADS)

Jarrell, Tiffany M.; Owen, Benjamin C.; Riedeman, James S.; Prentice, Boone M.; Pulliam, Chris J.; Max, Joann; Kenttämaa, Hilkka I.

2017-06-01

Laser-induced acoustic desorption (LIAD) allows for desorption of neutral nonvolatile compounds independent of their volatility or thermal stability. Many different ionization methods have been coupled with LIAD. Hence, this setup provides a better control over the types of ions formed than other mass spectrometry evaporation/ionization methods commonly used to characterize biomolecules, such as ESI or MALDI. In this study, the utility of LIAD coupled with electron ionization (EI) was tested for the analysis of common amino acids with no derivatization. The results compared favorably with previously reported EI mass spectra obtained using thermal desorption/EI. Further, LIAD/EI mass spectra collected for hydrochloride salts of two amino acids were found to be similar to those measured for the neutral amino acids with the exception of the appearance of an HCl+● ion. However, the hydrochloride salt of arginine showed a distinctly different LIAD/EI mass spectrum than the previously published literature EI mass spectrum, likely due to its highly basic side chain that makes a specific zwitterionic form particularly favorable. Finally, EI mass spectra were measured for seven small peptides, including di-, tri-, and tetrapeptides. These mass spectra show a variety of ion types. However, an type ions are prevalent. Also, electron-induced dissociation (EID) of protonated peptides has been reported to form primarily an type ions. In addition, the loss of small neutral molecules and side-chain cleavages were observed that are reminiscent of other high-energy fragmentation methods, such as EID. Finally, the isomeric dipeptides LG and IG were found to produce drastically different EI mass spectra, thus allowing differentiation of the leucine and isoleucine amino acids in these dipeptides. [Figure not available: see fulltext.

Wavelength-dependent UV photodesorption of pure N2 and O2 ices

NASA Astrophysics Data System (ADS)

Fayolle, E. C.; Bertin, M.; Romanzin, C.; Poderoso, H. A. M.; Philippe, L.; Michaut, X.; Jeseck, P.; Linnartz, H.; Öberg, K. I.; Fillion, J.-H.

2013-08-01

Context. Ultraviolet photodesorption of molecules from icy interstellar grains can explain observations of cold gas in regions where thermal desorption is negligible. This non-thermal desorption mechanism should be especially important where UV fluxes are high. Aims: N2 and O2 are expected to play key roles in astrochemical reaction networks, both in the solid state and in the gas phase. Measurements of the wavelength-dependent photodesorption rates of these two infrared-inactive molecules provide astronomical and physical-chemical insights into the conditions required for their photodesorption. Methods: Tunable radiation from the DESIRS beamline at the SOLEIL synchrotron in the astrophysically relevant 7 to 13.6 eV range is used to irradiate pure N2 and O2 thin ice films. Photodesorption of molecules is monitored through quadrupole mass spectrometry. Absolute rates are calculated by using the well-calibrated CO photodesorption rates. Strategic N2 and O2 isotopolog mixtures are used to investigate the importance of dissociation upon irradiation. Results: N2 photodesorption mainly occurs through excitation of the b1Πu state and subsequent desorption of surface molecules. The observed vibronic structure in the N2 photodesorption spectrum, together with the absence of N3 formation, supports that the photodesorption mechanism of N2 is similar to CO, i.e., an indirect DIET (Desorption Induced by Electronic Transition) process without dissociation of the desorbing molecule. In contrast, O2 photodesorption in the 7-13.6 eV range occurs through dissociation and presents no vibrational structure. Conclusions: Photodesorption rates of N2 and O2 integrated over the far-UV field from various star-forming environments are lower than for CO. Rates vary between 10-3 and 10-2 photodesorbed molecules per incoming photon.

Promising SiC support for Pd catalyst in selective hydrogenation of acetylene to ethylene

NASA Astrophysics Data System (ADS)

Guo, Zhanglong; Liu, Yuefeng; Liu, Yan; Chu, Wei

2018-06-01

In this study, SiC supported Pd nanoparticles were found to be an efficient catalyst in acetylene selective hydrogenation reaction. The ethylene selectivity can be about 20% higher than that on Pd/TiO2 catalyst at the same acetylene conversion at 90%. Moreover, Pd/SiC catalyst showed a stable catalytic life at 65 °C with 80% ethylene selectivity. With the detailed characterization using temperature-programmed reduction (H2-TPR), powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N2 adsorption/desorption analysis, CO-chemisorption and thermo-gravimetric analysis (TGA), it was found that SiC owns a lower surface area (22.9 m2/g) and a broad distribution of meso-/macro-porosity (from 5 to 65 nm), which enhanced the mass transfer during the chemical process at high reaction rate and decreased the residence time of ethylene on catalyst surface. Importantly, SiC support has the high thermal conductivity, which favored the rapid temperature homogenization through the catalyst bed and inhabited the over-hydrogenation of acetylene. The surface electronic density of Pd on Pd/SiC catalyst was higher than that on Pd/TiO2, which could promote desorption of ethylene from surface of the catalyst. TGA results confirmed a much less coke deposition on Pd/SiC catalyst.

Thermal expansion of composites: Methods and results. [large space structures

NASA Technical Reports Server (NTRS)

Bowles, D. E.; Tenney, D. R.

1981-01-01

The factors controlling the dimensional stability of various components of large space structures were investigated. Cyclic, thermal and mechanical loading were identified as the primary controlling factors of the dimensional stability of cables. For organic matrix composites, such as graphite-epoxy, it was found that these factors include moisture desorption in the space environment, thermal expansion as the structure moves from the sunlight to shadow in its orbit, mechanical loading, and microyielding of the material caused by microcracking of the matrix material. The major focus was placed on the thermal expansion of composites and in particular the development and testing of a method for its measurement.

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.

Adsorption of NO on alumina-supported oxides and oxide-hydroxides of manganese.

PubMed

Spasova, I; Nikolov, P; Mehandjiev, D

2005-10-15

The adsorption capacity for NO of alumina-supported oxides and oxide-hydroxides of manganese have been studied. Two series of samples have been prepared by precipitation on gamma-alumina and appropriate thermal treatment. The samples have been characterized by adsorption methods, magnetic methods, electronic paramagnetic resonance (EPR), transient response technique, and temperature-programmed desorption (TPD). The influence of the concentration of the initial manganese-containing solution has been investigated. The sample, prepared with a solution with Mn concentration of 4 g/100 ml, has been shown to be the best adsorbent for NO under the conditions of the experiment. It has been found that the presence mainly of Mn3+ ions on the surface of the support is probably responsible for the enhanced adsorption capacity.

Assessment of a new method for the analysis of decomposition gases of polymers by a combining thermogravimetric solid-phase extraction and thermal desorption gas chromatography mass spectrometry.

PubMed

Duemichen, E; Braun, U; Senz, R; Fabian, G; Sturm, H

2014-08-08

For analysis of the gaseous thermal decomposition products of polymers, the common techniques are thermogravimetry, combined with Fourier transformed infrared spectroscopy (TGA-FTIR) and mass spectrometry (TGA-MS). These methods offer a simple approach to the decomposition mechanism, especially for small decomposition molecules. Complex spectra of gaseous mixtures are very often hard to identify because of overlapping signals. In this paper a new method is described to adsorb the decomposition products during controlled conditions in TGA on solid-phase extraction (SPE) material: twisters. Subsequently the twisters were analysed with thermal desorption gas chromatography mass spectrometry (TDS-GC-MS), which allows the decomposition products to be separated and identified using an MS library. The thermoplastics polyamide 66 (PA 66) and polybutylene terephthalate (PBT) were used as example polymers. The influence of the sample mass and of the purge gas flow during the decomposition process was investigated in TGA. The advantages and limitations of the method were presented in comparison to the common analysis techniques, TGA-FTIR and TGA-MS. Copyright © 2014 Elsevier B.V. All rights reserved.

Thin-layer chromatography and mass spectrometry coupled using proximal probe thermal desorption with electrospray or atmospheric pressure chemical ionization.

PubMed

Ovchinnikova, Olga S; Van Berkel, Gary J

2010-06-30

An atmospheric pressure proximal probe thermal desorption sampling method coupled with secondary ionization by electrospray or atmospheric pressure chemical ionization was demonstrated for the mass spectrometric analysis of a diverse set of compounds (dyestuffs, pharmaceuticals, explosives and pesticides) separated on various high-performance thin-layer chromatography plates. Line scans along or through development lanes on the plates were carried out by moving the plate relative to a stationary heated probe positioned close to or just touching the stationary phase surface. Vapors of the compounds thermally desorbed from the surface were drawn into the ionization region of a combined electrospray ionization/atmospheric pressure chemical ionization source where they merged with reagent ions and/or charged droplets from a corona discharge or an electrospray emitter and were ionized. The ionized components were then drawn through the atmospheric pressure sampling orifice into the vacuum region of a triple quadrupole mass spectrometer and detected using full scan, single ion monitoring, or selected reaction monitoring mode. Studies of variable parameters and performance metrics including the proximal probe temperature, gas flow rate into the ionization region, surface scan speed, read-out resolution, detection limits, and surface type are discussed.

Application of zeolitic material synthesized from thermally treated sediment to the removal of trivalent chromium from wastewater.

PubMed

Guan, Qingyu; Wu, Deyi; Lin, Yan; Chen, Xuechu; Wang, Xinze; Li, Chunjie; He, Shengbing; Kong, Hainan

2009-08-15

Zeolitic materials were synthesized from thermally treated sediment by alkali treatment using different NaOH/sediment ratios. Characterization of the materials was done by XRD, FTIR, cation exchange capacity and specific surface area. Use of high NaOH/sediment ratio favored the formation of zeolite. The potential value of the zeolitic materials for the retention of trivalent chromium from water was examined. The maximum of Cr(III) sorption by the zeolitic materials, determined by a repeated batch equilibration method, ranged from 38.9 to 75.8 mg/g which was much greater than that of the thermally treated sediment (6.3 mg/g). No release of sorbed Cr(III) by 1.0M MgCl(2) at pH 7 was observed but Cr(III) desorption by ionic electrolyte increased with decreasing pH. The zeolitic materials could completely remove Cr(III) from wastewater even in the presence of Na(+) and Ca(2+) with high concentrations with a dose above 2.5 g/L. The pH-dependent desorption behavior and the high selectivity of zeolitic material for Cr(III) were explained by sorption at surface hydroxyl sites and formation of surface precipitates.

Modeling Deuterium Release from Plasma Implanted Surfaces

NASA Astrophysics Data System (ADS)

Grossman, A. A.; Doerner, R.; Hirooka, Y.; Luckhardt, S. C.; Sze, F. C.

1997-11-01

When energetic ions or atoms of hydrogen isotopes interact with a solid surface, they may either be reflected or they may be implanted, a slowing down process within the subsurface layer of the energetic particles to thermal velocities. Subsequent interactions of the thermalized particles are those of diffusion and trapping within the material and the possibility of re-emission from the solid via desorption. The diffusion equation and its boundary conditions govern the transport of this thermalized hydrogen within the material. Diffusivities obey an Arrhenius law over as much as fourteen orders of magnitude for the temperature range of interest for a fusion reactor first wall and divertor plate. Using TMAP4, a variety of diffusion models are set up for comparison with experiments on PISCES which involve implantation and desorption of deuterium from beryllium, tungsten, carbon and boron carbide. The parameters and characteristics of the models which give the closest fit to the experimental data are reported. At the high fluences of these experiments, it is necessary to take into account saturation effects during implantation using a separate implantation layer with thickness given by TRIM and a higher trapping to lattice ratio than in the bulk in order to model the experimental data.

Surface chemistry relevant to material processing for semiconductor devices

NASA Astrophysics Data System (ADS)

Okada, Lynne Aiko

Metal-oxide-semiconductor (MOS) structures are the core of many modern integrated circuit (IC) devices. Each material utilized in the different regions of the device has its own unique chemistry. Silicon is the base semiconductor material used in the majority of these devices. With IC device complexity increasing and device dimensions decreasing, understanding material interactions and processing becomes increasingly critical. Hsb2 desorption is the rate-limiting step in silicon growth using silane under low temperature conditions. Activation energies for Hsb2 desorption measured during Si chemical vapor deposition (CVD) versus single-crystal studies are found to be significantly lower. It has been proposed that defect sites on the silicon surface could explain the observed differences. Isothermal Hsb2 desorption studies using laser induced thermal desorption (LITD) techniques have addressed this issue. The growth of low temperature oxides is another relevant issue for fabrication of IC devices. Recent studies using 1,4-disilabutane (DSB) (SiHsb3CHsb2CHsb2SiHsb3) at 100sp°C in ambient Osb2 displayed the successful low temperature growth of silicon dioxide (SiOsb2). However, these studies provided no information about the deposition mechanism. We performed LITD and Fourier transform infrared (FTIR) studies on single-crystal and porous silicon surfaces to examine the adsorption, decomposition, and desorption processes to determine the deposition mechanism. Titanium nitride (TiN) diffusion barriers are necessary in modern metallization structures. Controlled deposition using titanium tetrachloride (TiClsb4) and ammonia (NHsb3) has been demonstrated using atomic layered processing (ALP) techniques. We intended to study the sequential deposition method by monitoring the surface intermediates using LITD techniques. However, formation of a Cl impurity source, ammonium chloride (NHsb4sp+Clsp-), was observed, thereby, limiting our ability for effective studies. Tetrakis(dimethylamino)titanium (Tilbrack N\\{CHsb3\\}sb2rbracksb4) (TDMAT) is another precursor used in the CVD deposition of TiN films in IC devices. Thermal decomposition studies have demonstrated deviations from conformal deposition. Successful conformal deposition may be affected by readsorption of the reaction product, dimethylamine (HNlbrack CHsb3rbracksb2). Detailed studies were performed using LITD techniques in order to understand the adsorption and desorption kinetics of TDMAT and dimethylamine to gain insights about the conformal deposition of TiN.

Diffusion coefficients of Fokker-Planck equation for rotating dust grains in a fusion plasma

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bakhtiyari-Ramezani, M., E-mail: mahdiyeh.bakhtiyari@gmail.com; Alinejad, N., E-mail: nalinezhad@aeoi.org.ir; Mahmoodi, J., E-mail: mahmoodi@qom.ac.ir

2015-11-15

In the fusion devices, ions, H atoms, and H{sub 2} molecules collide with dust grains and exert stochastic torques which lead to small variations in angular momentum of the grain. By considering adsorption of the colliding particles, thermal desorption of H atoms and normal H{sub 2} molecules, and desorption of the recombined H{sub 2} molecules from the surface of an oblate spheroidal grain, we obtain diffusion coefficients of the Fokker-Planck equation for the distribution function of fluctuating angular momentum. Torque coefficients corresponding to the recombination mechanism show that the nonspherical dust grains may rotate with a suprathermal angular velocity.

Extraction Techniques for Polycyclic Aromatic Hydrocarbons in Soils

PubMed Central

Lau, E. V.; Gan, S.; Ng, H. K.

2010-01-01

This paper aims to provide a review of the analytical extraction techniques for polycyclic aromatic hydrocarbons (PAHs) in soils. The extraction technologies described here include Soxhlet extraction, ultrasonic and mechanical agitation, accelerated solvent extraction, supercritical and subcritical fluid extraction, microwave-assisted extraction, solid phase extraction and microextraction, thermal desorption and flash pyrolysis, as well as fluidised-bed extraction. The influencing factors in the extraction of PAHs from soil such as temperature, type of solvent, soil moisture, and other soil characteristics are also discussed. The paper concludes with a review of the models used to describe the kinetics of PAH desorption from soils during solvent extraction. PMID:20396670

Diffusion coefficients of Fokker-Planck equation for rotating dust grains in a fusion plasma

NASA Astrophysics Data System (ADS)

Bakhtiyari-Ramezani, M.; Mahmoodi, J.; Alinejad, N.

2015-11-01

In the fusion devices, ions, H atoms, and H2 molecules collide with dust grains and exert stochastic torques which lead to small variations in angular momentum of the grain. By considering adsorption of the colliding particles, thermal desorption of H atoms and normal H2 molecules, and desorption of the recombined H2 molecules from the surface of an oblate spheroidal grain, we obtain diffusion coefficients of the Fokker-Planck equation for the distribution function of fluctuating angular momentum. Torque coefficients corresponding to the recombination mechanism show that the nonspherical dust grains may rotate with a suprathermal angular velocity.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 (Papermore » 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.« less

COMPARISON OF MEASUREMENTS OF AMBIENT PARTICLE NITRATE WITH SEMI-CONTINUOUS INSTRUMENTS

EPA Science Inventory

Comparisons between two different semi-continuous monitors of ambient level particulate nitrate are interpreted for both field and laboratory studies. One instrument involves thermal desorption of particulate nitrate to form a combination of NO and NO2 gases which are detected ...

Direct Detection of Pharmaceuticals and Personal Care Products from Aqueous Samples with Thermally-Assisted Desorption Electrospray Ionization Mass Spectrometry

NASA Astrophysics Data System (ADS)

Campbell, Ian S.; Ton, Alain T.; Mulligan, Christopher C.

2011-07-01

An ambient mass spectrometric method based on desorption electrospray ionization (DESI) has been developed to allow rapid, direct analysis of contaminated water samples, and the technique was evaluated through analysis of a wide array of pharmaceutical and personal care product (PPCP) contaminants. Incorporating direct infusion of aqueous sample and thermal assistance into the source design has allowed low ppt detection limits for the target analytes in drinking water matrices. With this methodology, mass spectral information can be collected in less than 1 min, consuming ~100 μL of total sample. Quantitative ability was also demonstrated without the use of an internal standard, yielding decent linearity and reproducibility. Initial results suggest that this source configuration is resistant to carryover effects and robust towards multi-component samples. The rapid, continuous analysis afforded by this method offers advantages in terms of sample analysis time and throughput over traditional hyphenated mass spectrometric techniques.

Analysis of chemical warfare agents. II. Use of thiols and statistical experimental design for the trace level determination of vesicant compounds in air samples.

PubMed

Muir, Bob; Quick, Suzanne; Slater, Ben J; Cooper, David B; Moran, Mary C; Timperley, Christopher M; Carrick, Wendy A; Burnell, Christopher K

2005-03-18

Thermal desorption with gas chromatography-mass spectrometry (TD-GC-MS) remains the technique of choice for analysis of trace concentrations of analytes in air samples. This paper describes the development and application of a method for analysing the vesicant compounds sulfur mustard and Lewisites I-III. 3,4-Dimercaptotoluene and butanethiol were used to spike sorbent tubes and vesicant vapours sampled; Lewisite I and II reacted with the thiols while sulfur mustard and Lewisite III did not. Statistical experimental design was used to optimise thermal desorption parameters and the optimum method used to determine vesicant compounds in headspace samples taken from a decontamination trial. 3,4-Dimercaptotoluene reacted with Lewisites I and II to give a common derivative with a limit of detection (LOD) of 260 microg m(-3), while the butanethiol gave distinct derivatives with limits of detection around 30 microg m(-3).

High-throughput trace analysis of explosives in water by laser diode thermal desorption/atmospheric pressure chemical ionization-tandem mass spectrometry.

PubMed

Badjagbo, Koffi; Sauvé, Sébastien

2012-07-03

Harmful explosives can accumulate in natural waters in the long term during their testing, usage, storage, and dumping and can pose a health risk to humans and the environment. For the first time, attachment of small anions to neutral molecules in laser diode thermal desorption/atmospheric pressure chemical ionization was systematically investigated for the direct determination of trace nitroaromatics, nitrate esters, and nitramine explosives in water. Using ammonium chloride as an additive improved the instrument response for all the explosives tested and promoted the formation of several characteristic adduct ions. The method performs well achieving good linearity over at least 2 orders of magnitude, with coefficients of determination greater than 0.995. The resulting limits of detection are in the range of 0.009-0.092 μg/L. River water samples were successfully analyzed by the proposed method with accuracy in the range of 96-98% and a response time of 15 s, without any further pretreatment or chromatographic separation.

Determination of trichloroanisole and trichlorophenol in wineries' ambient air by passive sampling and thermal desorption-gas chromatography coupled to tandem mass spectrometry.

PubMed

Camino-Sánchez, F J; Bermúdez-Peinado, R; Zafra-Gómez, A; Ruíz-García, J; Vílchez-Quero, J L

2015-02-06

The present paper describes the calibration of selected passive samplers used in the quantitation of trichlorophenol and trichloroanisole in wineries' ambient air, by calculating the corresponding sampling rates. The method is based on passive sampling with sorbent tubes and involves thermal desorption-gas chromatography-triple quadrupole mass spectrometry analysis. Three commercially available sorbents were tested using sampling cartridges with a radial design instead of axial ones. The best results were found for Tenax TA™. Sampling rates (R-values) for the selected sorbents were determined. Passive sampling was also used for accurately determining the amount of compounds present in the air. Adequate correlation coefficients between the mass of the target analytes and exposure time were obtained. The proposed validated method is a useful tool for the early detection of trichloroanisole and its precursor trichlorophenol in wineries' ambient air while avoiding contamination of wine or winery facilities. Copyright © 2015 Elsevier B.V. All rights reserved.

Optimization and Validation of Thermal Desorption Gas Chromatography-Mass Spectrometry for the Determination of Polycyclic Aromatic Hydrocarbons in Ambient Air

PubMed Central

Durana, Nieves; García, José Antonio; Gómez, María Carmen; Alonso, Lucio

2018-01-01

Thermal desorption (TD) coupled with gas chromatography/mass spectrometry (TD-GC/MS) is a simple alternative that overcomes the main drawbacks of the solvent extraction-based method: long extraction times, high sample manipulation, and large amounts of solvent waste. This work describes the optimization of TD-GC/MS for the measurement of airborne polycyclic aromatic hydrocarbons (PAHs) in particulate phase. The performance of the method was tested by Standard Reference Material (SRM) 1649b urban dust and compared with the conventional method (Soxhlet extraction-GC/MS), showing a better recovery (mean of 97%), precision (mean of 12%), and accuracy (±25%) for the determination of 14 EPA PAHs. Furthermore, other 15 nonpriority PAHs were identified and quantified using their relative response factors (RRFs). Finally, the proposed method was successfully applied for the quantification of PAHs in real 8 h-samples (PM10), demonstrating its capability for determination of these compounds in short-term monitoring. PMID:29854561

Direct detection of pharmaceuticals and personal care products from aqueous samples with thermally-assisted desorption electrospray ionization mass spectrometry.

PubMed

Campbell, Ian S; Ton, Alain T; Mulligan, Christopher C

2011-07-01

An ambient mass spectrometric method based on desorption electrospray ionization (DESI) has been developed to allow rapid, direct analysis of contaminated water samples, and the technique was evaluated through analysis of a wide array of pharmaceutical and personal care product (PPCP) contaminants. Incorporating direct infusion of aqueous sample and thermal assistance into the source design has allowed low ppt detection limits for the target analytes in drinking water matrices. With this methodology, mass spectral information can be collected in less than 1 min, consuming ~100 μL of total sample. Quantitative ability was also demonstrated without the use of an internal standard, yielding decent linearity and reproducibility. Initial results suggest that this source configuration is resistant to carryover effects and robust towards multi-component samples. The rapid, continuous analysis afforded by this method offers advantages in terms of sample analysis time and throughput over traditional hyphenated mass spectrometric techniques.

Ni-catalysed WO3 nanostructures grown by electron beam rapid thermal annealing for NO2 gas sensing

NASA Astrophysics Data System (ADS)

Chandrasekaran, Gopalakrishnan; Sundararaj, Anuraj; Therese, Helen Annal; Jeganathan, K.

2015-07-01

Ni-catalysed WO3 (Ni-WO3) nanowires and nanosheets were grown on Si (100) substrates using electron beam evaporation followed by electron beam-assisted rapid thermal annealing process. Gas-sensing measurements were performed for various concentrations of NO2 in dry air at a temperature range of 50-400 °C. Nanowires and nanosheets show optimum sensor response of 229 and 197 at operating temperatures of 200 and 250 °C, respectively, for 100 ppm of NO2 exposure. Nanowires demonstrated a rapid response time of 66 s, but a slow recovery time of 204 s owing to poor rate of desorption of the adsorbed NO2 gas molecules from the internal porous structure of nanowires. In contrast, the recovery time for nanosheet was 126 s due to higher desorption rate of the adhered NO2 molecules associated with low surface area and less porous structure of nanosheet. The gas-sensing mechanism of WO3 nanostructure is discussed briefly.

The Influence of Microstructure on Deuterium Retention in Polycrystalline Tungsten

DOE PAGES

Garrison, Lauren M.; Meyer, Fred W.; Bannister, Mark E.

2017-09-18

The retention of hydrogen isotopes in the plasma-facing materials of a fusion reactor is dependent on the density of trapping sites in the material. One factor that can influence the trapping defects is the surface state of the material before exposure. Mechanically polished, electropolished, and recrystallized tungsten samples were compared by exposing them to 350 eV D + beams with peak fluences of ~1 × 10 24 D +/m 2 at 500 and 740 K at the Multicharged Ion Research Facility (MIRF). At the exposure temperature of 740 K, no significant retention was detected. For material exposed at 500 K,more » significant differences in retention were observed, and the order of increasing retention was recrystallized, electropolished, and mechanically polished. Lastly, the other variable besides surface treatment was the time delay between ion exposure and thermal desorption spectroscopy which also may have impacted the retention measurements if there was out-gassing of the D while samples were in storage before thermal desorption spectroscopy (TDS).« less

Superfund Record of Decision (EPA Region 4): Aberdeen Pesticide Dumps, Moore County, Aberdeen, NC. (First remedial action), (Amendment), September 1991

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1991-09-30

The Aberdeen Pesticide Dumps site consists of a plant area and four disposal areas in Aberdeen, Moore County, North Carolina. The five areas are Farm Chemicals, Twin Sites, Fairway Six, McIver Dump, and Route 211. Ground water is the main source of drinking water for local residents. After investigations by EPA's Emergency Response Section in 1985 and 1986, several removal actions were conducted, including removing surface contaminants, drums, and soil in several areas. The ROD concurrently addresses surface and subsurface soil contamination. The amended remedial action for this site includes conducting a treatability study using thermal desorption; excavating and treatingmore » a total of 123,933 cubic yards of soil from all five areas including previously excavated soil from the Fairway Six and McIver Dump areas using an onsite thermal desorption process that includes an activated carbon adsorption to treat off-gases, followed by offsite incineration of residual organics.« less

A hot implantation study on the evolution of defects in He ion implanted MgO(1 0 0)

NASA Astrophysics Data System (ADS)

Fedorov, A. V.; van Huis, M. A.; van Veen, A.

2002-05-01

Ion implantation at elevated temperature, so-called hot implantation, was used to study nucleation and thermal stability of the defects. In this work, MgO(1 0 0) single crystal samples were implanted with 30 keV He ions at various implantation temperatures. The implantation doses ranged from 10 14 to 10 16 cm -2. The implantation introduced defects were subsequently studied by thermal helium desorption spectroscopy (THDS) and Doppler broadening positron beam analysis (PBA). The THDS study provides vital information on the kinetics of He release from the sample. PBA technique, being sensitive to the open volume defects, provides complementary information on cavity evolution. The THD study has shown that in most cases helium release is characterised by the activation energy of Q=4.7±0.5 eV with the maximum release temperature of Tmax=1830 K. By applying first order desorption model the pre-exponent factor is estimated as ν=4.3×10 11 s -1.

Thermal desorption of hydrogen from Mg2Ni hydrogen storage materials.

PubMed

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

2011-07-01

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

Auto-ignition of methane-air mixtures flowing along an array of thin catalytic plates

NASA Astrophysics Data System (ADS)

Treviño, C.

2010-12-01

In this paper, the heterogeneous ignition of a methane-air mixture flowing along an infinite array of catalytic parallel plates has been studied by inclusion of gas expansion effects and the finite heat conduction on the plates. The system of equations considers the full compressible Navier-Stokes equations coupled with the energy equations of the plates. The gas expansion effects which arise from temperature changes have been considered. The heterogeneous kinetics considers the adsorption and desorption reactions for both reactants. The limits of large and small longitudinal thermal conductance of the plate material are analyzed and the critical conditions for ignition are obtained in closed form. The governing equations are solved numerically using finite differences. The results show that ignition is more easily produced as the longitudinal wall thermal conductance increases, and the effects of the gas expansion on the catalytic ignition process are rather small due to the large value of the activation energy of the desorption reaction of adsorbed oxygen atoms.

Analyses of the wood preservative component N-cyclohexyl-diazeniumdioxide in impregnated pine sapwood by direct thermal desorption-gas chromatography-mass spectrometry.

PubMed

Jüngel, Peter; de Koning, Sjaak; Brinkman, Udo A Th; Melcher, Eckhard

2002-04-12

Investigations concerning the qualitative and quantitative determination of the organic wood preservative component N-cyclohexyl-diazeniumdioxide (HDO) in treated timber were carried out by means of direct thermal desorption-gas chromatography-mass spectrometry (DTD-GC-MS). It could be shown that the identification of HDO in treated pine sapwood (Pinus sylyestris L.) is relatively simple using this analytical technique. Quantification of this active ingredient can be carried out using the peak area of the specific mass fragment m/z 114. A calibration curve with a high correlation coefficient was obtained in the range from 40 to 550 mg HDO per kg timber. Furthermore it can be deduced that the results obtained are characterised by an excellent reproducibility with standard deviations ranging from 5 to 10% in general. For the chosen experimental set up a detection limit of 4 mg HDO per kg treated pine sapwood was calculated, although merely 20% of the active ingredient was desorbed.

The Influence of Microstructure on Deuterium Retention in Polycrystalline Tungsten

DOE Office of Scientific and Technical Information (OSTI.GOV)

Garrison, Lauren M.; Meyer, Fred W.; Bannister, Mark E.

The retention of hydrogen isotopes in the plasma-facing materials of a fusion reactor is dependent on the density of trapping sites in the material. One factor that can influence the trapping defects is the surface state of the material before exposure. Mechanically polished, electropolished, and recrystallized tungsten samples were compared by exposing them to 350 eV D + beams with peak fluences of ~1 × 10 24 D +/m 2 at 500 and 740 K at the Multicharged Ion Research Facility (MIRF). At the exposure temperature of 740 K, no significant retention was detected. For material exposed at 500 K,more » significant differences in retention were observed, and the order of increasing retention was recrystallized, electropolished, and mechanically polished. Lastly, the other variable besides surface treatment was the time delay between ion exposure and thermal desorption spectroscopy which also may have impacted the retention measurements if there was out-gassing of the D while samples were in storage before thermal desorption spectroscopy (TDS).« less

High translational energy release in H2 (D2) associative desorption from H (D) chemisorbed on C(0001).

PubMed

Baouche, S; Gamborg, G; Petrunin, V V; Luntz, A C; Baurichter, A; Hornekaer, L

2006-08-28

Highly energetic translational energy distributions are reported for hydrogen and deuterium molecules desorbing associatively from the atomic chemisorption states on highly oriented pyrolytic graphite (HOPG). Laser assisted associative desorption is used to measure the time of flight of molecules desorbing from a hydrogen (deuterium) saturated HOPG surface produced by atomic exposure from a thermal atom source at around 2100 K. The translational energy distributions normal to the surface are very broad, from approximately 0.5 to approximately 3 eV, with a peak at approximately 1.3 eV. The highest translational energy measured is close to the theoretically predicted barrier height. The angular distribution of the desorbing molecules is sharply peaked along the surface normal and is consistent with thermal broadening contributing to energy release parallel to the surface. All results are in qualitative agreement with recent density functional theory calculations suggesting a lowest energy para-type dimer recombination path.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, R. Scott; Li, Zhenjun; Dohnalek, Zdenek

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 thesemore » 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.« less

Chemometric studies for the characterization and differentiation of microorganisms using in situ derivatization and thermal desorption ion mobility spectrometry.

PubMed

Ochoa, Mariela L; Harrington, Peter B

2005-02-01

Whole-cell bacteria were characterized and differentiated by thermal desorption ion mobility spectrometry and chemometric modeling. Principal component analysis was used to evaluate the differences in the ion mobility spectra of whole-cell bacteria and the fatty acid methyl esters (FAMEs) generated in situ after derivatization of the bacterial lipids. Alternating least squares served to extract bacterial peaks from the complex ion mobility spectra of intact microorganisms and, therefore, facilitated the characterization of bacterial strains, species, and Gram type. In situ thermal hydrolysis/methylation with tetramethylammonium hydroxide was necessary for the differentiation of Escherichia coli strains, which otherwise could not be distinguished by spectra acquired with the ITEMISER ion mobility spectrometer. The addition of the methylating agent had no effect on Gram-positive bacteria, and therefore, they could not be differentiated by genera. The classification of E. coli strains was possible by analysis of the IMS spectra from the FAMEs generated in situ. By using the fuzzy multivariate rule-building expert system and cross-validation, a correct classification rate of 96% (22 out of 23 spectra) was obtained. Chemometric modeling on bacterial ion mobility spectra coupled to thermal hydrolysis/methylation proved a simple, rapid (2 min/sample), inexpensive, and sensitive technique to characterize and differentiate intact microorganisms. The ITEMISER ion mobility spectrometer could detect as few as 4 x 10(6) cells/sample.

Surface Response of Brominated Carbon Media on Laser and Thermal Excitation: Optical and Thermal Analysis Study.

PubMed

Multian, Volodymyr V; Kinzerskyi, Fillip E; Vakaliuk, Anna V; Grishchenko, Liudmyla M; Diyuk, Vitaliy E; Boldyrieva, Olga Yu; Kozhanov, Vadim O; Mischanchuk, Oleksandr V; Lisnyak, Vladyslav V; Gayvoronsky, Volodymyr Ya

2017-12-01

The present study is objected to develop an analytical remote optical diagnostics of the functionalized carbons surface. Carbon composites with up to 1 mmol g -1 of irreversibly adsorbed bromine were produced by the room temperature plasma treatment of an activated carbon fabric (ACF) derived from polyacrylonitrile textile. The brominated ACF (BrACF) was studied by elastic optical scattering indicatrix analysis at wavelength 532 nm. The obtained data were interpreted within results of the thermogravimetric analysis, X-ray photoelectron spectroscopy and temperature programmed desorption mass spectrometry. The bromination dramatically reduces the microporosity producing practically non-porous material, while the incorporated into the micropores bromine induces the dielectric and structural impact on surface polarizability and conductivity due to the charging effect. We have found that the elastic optical scattering in proper solid angles in the forward and the backward hemispheres is sensitive to the kind of the bromine bonding, e.g., physical adsorption or chemisorption, and the bromination level, respectively, that can be utilized for the express remote fabrication control of the nanoscale carbons with given interfaces.

Using Temperature-Dependent Phenomena at Oxide Surfaces for Species Recognition in Chemical Sensing.

NASA Astrophysics Data System (ADS)

Semancik, Steve; Meier, Douglas; Evju, Jon; Benkstein, Kurt; Boger, Zvi; Montgomery, Chip

2006-03-01

Nanostructured films of SnO2 and TiO2 have been deposited on elements in MEMS arrays to fabricate solid state conductometric gas microsensors. The multilevel platforms within an array, called microhotplates, are individually addressable for localized temperature control and measurement of sensing film electrical conductance. Temperature variations of the microhotplates are employed in thermally-activated CVD oxide film growth, and for rapid temperature-programmed operation of the microsensors. Analytical information on environmental gas phase composition is produced temporally as purposeful thermal fluctuations provide energetic and kinetic control of surface reaction and adsorption/desorption phenomena. Resulting modulations of oxide adsorbate populations cause changing charge transfer behavior and measurable conductance responses. Rich data streams from different sensing films in the arrays have been analyzed by Artificial Neural Networks (ANN) to successfully recognize low concentration species in mixed gases. We illustrate capabilities of the approach and technology in the homeland security area, where dangerous chemicals (TICs, CWSs and CWAs) have been detected at 10-100 ppb levels in interference-spiked air backgrounds.

DOE Office of Scientific and Technical Information (OSTI.GOV)

El-Atwani, Osman; Taylor, Chase N.; Frishkoff, James

Here, microstructural changes due to displacement damage and helium desorption are two phenomena that occur in tungsten plasma facing materials in fusion reactors. Nanocrystalline metals are being investigated as radiation tolerant materials that can mitigate these microstructural changes and better trap helium along their grain boundaries. Here, we investigate the performance of three tungsten grades (nanocrystalline, ultrafine and ITER grade tungsten), exposed to a high fluence of 4 keV helium at both RT and 773 K, during a thermal desorption spectroscopy (TDS) experiment. An investigation of the microstructure in pre-and post-TDS sample sets was performed. The amount of desorbed heliummore » was shown to be highest in the ITER grade tungsten and lowest in the nanocrystalline tungsten. Correlating the desorption spectra and the microstructure (grain boundaries decorated with nanopores and crack formation) and comparing with previous literature on coarse grained tungsten samples at similar irradiation and TDS conditions, revealed the importance of grain boundaries in trapping helium and limiting helium desorption up to a high temperature of 1350 K in agreement with transmission electron microscopy studies on helium irradiated tungsten which showed preferential and large facetted bubble formation along the grain boundaries in the nanocrystalline tungsten grade.« less

Brominated Tyrosine and Polyelectrolyte Multilayer Analysis by Laser Desorption VUV Postionization and Secondary Ion Mass Spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

University of Illinois at Chicago; Blaze, Melvin M. T.; Takahashi, Lynelle

2011-03-14

The small molecular analyte 3,5-dibromotyrosine (Br2Y) and chitosan-alginate polyelectrolyte multilayers (PEM) with and without adsorbed Br2Y were analyzed by laser desorption postionization mass spectrometry (LDPI-MS). LDPI-MS using 7.87 eV laser and tunable 8 ? 12.5 eV synchrotron vacuum ultraviolet (VUV) radiation found that desorption of clusters from Br2Y films allowed detection by≤8 eV single photon ionization. Thermal desorption and electronic structure calculations determined the ionization energy of Br2Y to be ~;;8.3?0.1 eV and further indicated that the lower ionization energies of clusters permitted their detection at≤8 eV photon energies. However, single photon ionization could only detect Br2Y adsorbed within PEMsmore » when using either higher photon energies or matrix addition to the sample. All samples were also analyzed by 25 keV Bi3 + secondary ion mass spectrometry (SIMS), with the negative ion spectra showing strong parent ion signal which complemented that observed by LDPI-MS. The negative ion SIMS depended strongly on the high electron affinity of this specific analyte and the analyte?s condensed phase environment.« less

Mechanisms of Nanophase-Induced Desorption in LDI-MS. A Short Review

PubMed Central

Picca, Rosaria Anna; Calvano, Cosima Damiana; Cioffi, Nicola; Palmisano, Francesco

2017-01-01

Nanomaterials are frequently used in laser desorption ionization mass spectrometry (LDI-MS) as DI enhancers, providing excellent figures of merit for the analysis of low molecular weight organic molecules. In recent years, literature on this topic has benefited from several studies assessing the fundamental aspects of the ion desorption efficiency and the internal energy transfer, in the case of model analytes. Several different parameters have been investigated, including the intrinsic chemical and physical properties of the nanophase (chemical composition, thermal conductivity, photo-absorption efficiency, specific heat capacity, phase transition point, explosion threshold, etc.), along with morphological parameters such as the nanophase size, shape, and interparticle distance. Other aspects, such as the composition, roughness and defects of the substrate supporting the LDI-active nanophases, the nanophase binding affinity towards the target analyte, the role of water molecules, have been taken into account as well. Readers interested in nanoparticle based LDI-MS sub-techniques (SALDI-, SELDI-, NALDI- MS) will find here a concise overview of the recent findings in the specialized field of fundamental and mechanistic studies, shading light on the desorption ionization phenomena responsible of the outperforming MS data offered by these techniques. PMID:28368330

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, Brønsted and Lewis acid sites were differentiated and the distribution of Brønsted 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. Copyright © 2013 The Chemical Society of Japan and Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Improved spatial resolution for spot sampling in thermal desorption atomic force microscopy – mass spectrometry via rapid heating functions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Somnath, Suhas; Jesse, Stephen; Van Berkel, Gary J.

The key to advancing materials is to understand and control their structure and chemistry. However, thorough chemical characterization is challenging since existing techniques characterize only a few properties of the specimen, thereby necessitating multiple measurement platforms to acquire the necessary information. The multimodal combination of atomic force microscopy (AFM) and mass spectrometry (MS) transcends existing analytical capabilities for nanometer scale spatially resolved correlation of the chemical and physical properties of a sample surface. One such hybrid system employs heated AFM cantilevers for thermal desorption (TD) sampling of molecules from a surface and subsequent gas phase ionization and detection of themore » liberated species by MS. Here in this paper, we report on the use of voltage pulse trains to tailor cantilever heating such that spot sampling size was reduced and mass spectral signal was improved compared to constant voltage, static heating of the cantilever. Desorption efficiency (DE), defined as the quotient of the mass spectral signal intensity and the volume of the desorption crater, was used to judge the effectiveness of a particular tailored heating function. To guide the development and optimization of the heating functions and aid in interpreting experimental results, a 1D finite element model was developed that predicted the cantilever response to different heating functions. Three tailored heating functions that used different combinations, magnitudes, and durations of rectangular voltage pulses, were used for surface spot sampling. The resultant sampling spot size and DE were compared to the same metrics obtained with the conventional method that uses a single voltage pulse. Using a model system composed of a thin film of ink containing pigment yellow 74 as a model system, desorption craters shrunk from 2 μm, using the conventional approach, to 310 nm using the optimum tailored heating function. This same pulsed heating function produced a 381× improvement in the DE and an 8× improvement in spatial resolution compared to the conventional heating approach showing that signal/amount of material sampled was improved significantly by this new cantilever heating strategy.« less

Improved spatial resolution for spot sampling in thermal desorption atomic force microscopy – mass spectrometry via rapid heating functions

DOE PAGES

Somnath, Suhas; Jesse, Stephen; Van Berkel, Gary J.; ...

2017-04-17

The key to advancing materials is to understand and control their structure and chemistry. However, thorough chemical characterization is challenging since existing techniques characterize only a few properties of the specimen, thereby necessitating multiple measurement platforms to acquire the necessary information. The multimodal combination of atomic force microscopy (AFM) and mass spectrometry (MS) transcends existing analytical capabilities for nanometer scale spatially resolved correlation of the chemical and physical properties of a sample surface. One such hybrid system employs heated AFM cantilevers for thermal desorption (TD) sampling of molecules from a surface and subsequent gas phase ionization and detection of themore » liberated species by MS. Here in this paper, we report on the use of voltage pulse trains to tailor cantilever heating such that spot sampling size was reduced and mass spectral signal was improved compared to constant voltage, static heating of the cantilever. Desorption efficiency (DE), defined as the quotient of the mass spectral signal intensity and the volume of the desorption crater, was used to judge the effectiveness of a particular tailored heating function. To guide the development and optimization of the heating functions and aid in interpreting experimental results, a 1D finite element model was developed that predicted the cantilever response to different heating functions. Three tailored heating functions that used different combinations, magnitudes, and durations of rectangular voltage pulses, were used for surface spot sampling. The resultant sampling spot size and DE were compared to the same metrics obtained with the conventional method that uses a single voltage pulse. Using a model system composed of a thin film of ink containing pigment yellow 74 as a model system, desorption craters shrunk from 2 μm, using the conventional approach, to 310 nm using the optimum tailored heating function. This same pulsed heating function produced a 381× improvement in the DE and an 8× improvement in spatial resolution compared to the conventional heating approach showing that signal/amount of material sampled was improved significantly by this new cantilever heating strategy.« less

Apparatus for thermal swing adsorption and thermally-enhanced pressure swing adsorption

DOEpatents

Wegeng, Robert S.; Rassat, Scot D.; Stenkamp, Victoria S.; TeGrotenhuis, Ward E.; Matson, Dean W.; Drost, M. Kevin; Viswanathan, Vilayanur V.

2005-12-13

The present invention provides compact adsorption systems that are capable of rapid temperature swings and rapid cycling. Novel methods of thermal swing adsorption and thermally-enhanced pressure swing adsorption are also described. In some aspects of the invention, a gas is passed through the adsorbent thus allowing heat exchangers to be very close to all portions of the adsorbent and utilize less space. In another aspect, the adsorption media is selectively heated, thus reducing energy costs. Methods and systems for gas adsorption/desorption having improved energy efficiency with capability of short cycle times are also described. Advantages of the invention include the ability to use (typically) 30-100 times less adsorbent compared to conventional systems.

Method for thermal swing adsorption and thermally-enhanced pressure swing adsorption

DOEpatents

Wegeng, Robert S.; Rassat, Scot D.; Stenkamp, Victoria S.; TeGrotenhuis, Ward E.; Matson, Dean W.; Drost, M. Kevin; Viswanathan, Vilayanur V.

2003-10-07

The present invention provides compact adsorption systems that are capable of rapid temperature swings and rapid cycling. Novel methods of thermal swing adsorption and thermally-enhanced pressure swing adsorption are also described. In some aspects of the invention, a gas is passed through the adsorbent thus allowing heat exchangers to be very close to all portions of the adsorbent and utilize less space. In another aspect, the adsorption media is selectively heated, thus reducing energy costs. Methods and systems for gas adsorption/desorption having improved energy efficiency with capability of short cycle times are also described. Advantages of the invention include the ability to use (typically) 30-100 times less adsorbent compared to conventional systems.

Retention and release of hydrogen isotopes in tungsten plasma-facing components: the role of grain boundaries and the native oxide layer from a joint experiment-simulation integrated approach

NASA Astrophysics Data System (ADS)

Hodille, E. A.; Ghiorghiu, F.; Addab, Y.; Založnik, A.; Minissale, M.; Piazza, Z.; Martin, C.; Angot, T.; Gallais, L.; Barthe, M.-F.; Becquart, C. S.; Markelj, S.; Mougenot, J.; Grisolia, C.; Bisson, R.

2017-07-01

Fusion fuel retention (trapping) and release (desorption) from plasma-facing components are critical issues for ITER and for any future industrial demonstration reactors such as DEMO. Therefore, understanding the fundamental mechanisms behind the retention of hydrogen isotopes in first wall and divertor materials is necessary. We developed an approach that couples dedicated experimental studies with modelling at all relevant scales, from microscopic elementary steps to macroscopic observables, in order to build a reliable and predictive fusion reactor wall model. This integrated approach is applied to the ITER divertor material (tungsten), and advances in the development of the wall model are presented. An experimental dataset, including focused ion beam scanning electron microscopy, isothermal desorption, temperature programmed desorption, nuclear reaction analysis and Auger electron spectroscopy, is exploited to initialize a macroscopic rate equation wall model. This model includes all elementary steps of modelled experiments: implantation of fusion fuel, fuel diffusion in the bulk or towards the surface, fuel trapping on defects and release of trapped fuel during a thermal excursion of materials. We were able to show that a single-trap-type single-detrapping-energy model is not able to reproduce an extended parameter space study of a polycrystalline sample exhibiting a single desorption peak. It is therefore justified to use density functional theory to guide the initialization of a more complex model. This new model still contains a single type of trap, but includes the density functional theory findings that the detrapping energy varies as a function of the number of hydrogen isotopes bound to the trap. A better agreement of the model with experimental results is obtained when grain boundary defects are included, as is consistent with the polycrystalline nature of the studied sample. Refinement of this grain boundary model is discussed as well as the inclusion in the model of a thin defective oxide layer following the experimental observation of the presence of an oxygen layer on the surface even after annealing to 1300 K.

Strategies for Monitoring the Performance of DNAPL Source Zone Remedies. Technical/Regulatory Guidelines

DTIC Science & Technology

2004-08-01

Vinegar , 2002; Bierschenk, et al., 2004; Baker and Kuhlman, 2002). It should be noted that the presence of even small amounts of liquid water will limit...Bioremediation of Trichloroethene.” Environmental Science and Technology, 36(10):2262–68. Stegemeier, G.L., and H.J. Vinegar . 2001. “Thermal Conduction...1134. Vinegar , H.J., G.L. Stegemeier, F.G. Carl, J.D. Stevenson, and R.J. Dudley. 1999. “In Situ Thermal Desorption of Soils Impacted with Chlorinated

Study on Desorption Process of n-Heptane and Methyl Cyclohexane Using UiO-66 with Hierarchical Pores.

PubMed

Chen, Sijia; Zhang, Lin; Zhang, Zhao; Qian, Gang; Liu, Zongjian; Cui, Qun; Wang, Haiyan

2018-06-06

UiO-66 (UiO for University of Oslo), is a zirconium-based MOF with reverse shape selectivity, gives an alternative way to produce high purity n-heptane used for the manufacture of high-purity pharmaceuticals. Couple of studies have shown that UiO-66 gives a high selectivity on the separation of n-/iso-alkanes. However, the microporous structure of UiO-66 causes poor mass transport during the desorption process. In this work, hierarchical-pore UiO-66 (H-UiO-66) was synthesized and utilized as an adsorbent of n-heptane (nHEP) and methyl cyclohexane (MCH) for systematically studying the desorption process of n/iso-alkanes. A suite of physical methods, including XRD patterns verified the UiO-66 structures and HRTEM showed the existence of hierarchical pores. N2 adsorption-desorption isotherms further confirmed the size distribution of hierarchical pores in H-UiO-66. Of particular note, the MCH/nHEP selectivity of H-UiO-66 is similar with UiO-66 in the same adsorption conditions, the desorption process of nHEP/MCH from H-UiO-66 is dramatically enhanced, viz, the desorption rates for nHEP/MCH from H-UiO-66 is enhanced by 30%/23% as comparing to UiO-66 at most. Moreover, desorption activation energy (Ed) derived from temperature-programmed desorption (TPD) experiments indicate that the Ed for nHEP/MCH is lower on H-UiO-66, i.e., the Ed of MCH on H-UiO-66 is ~37% lower than that on UiO-66 at most, leading to a milder condition for the desorption process. The introduction of hierarchical structures will be applicable for the optimization of desorption process during separation on porous materials.

Mass Spectrometry of Large, Fragile, and Involatile Molecules.

ERIC Educational Resources Information Center

Busch, Kenneth L.; Cooks, R. Graham

1982-01-01

Desorption ionization (DI) is used to obtain mass spectra of molecules whose vaporization by heating may lead to thermal degradation. Discusses DI techniques, characteristics of DI mass spectra, ion production, current applications of DI in mass spectroscopy, developments in DI, and prospects for future evolution of new DI techniques. (Author/JN)

Statistical Analysis of PDF's for Na Released by Photons from Solid Surfaces

NASA Astrophysics Data System (ADS)

Gamborino, D.; Wurz, P.

2018-05-01

We analyse the adequacy of three model speed PDF's previously used to describe the desorption of Na from a solid surface either by ESD or PSD. We found that the Maxwell PDF is too wide compared to measurements and non-thermal PDF's are better suited.

Laser-based methods for the analysis of low molecular weight compounds in biological matrices.

PubMed

Kiss, András; Hopfgartner, Gérard

2016-07-15

Laser-based desorption and/or ionization methods play an important role in the field of the analysis of low molecular-weight compounds (LMWCs) because they allow direct analysis with high-throughput capabilities. In the recent years there were several new improvements in ionization methods with the emergence of novel atmospheric ion sources such as laser ablation electrospray ionization or laser diode thermal desorption and atmospheric pressure chemical ionization and in sample preparation methods with the development of new matrix compounds for matrix-assisted laser desorption/ionization (MALDI). Also, the combination of ion mobility separation with laser-based ionization methods starts to gain popularity with access to commercial systems. These developments have been driven mainly by the emergence of new application fields such as MS imaging and non-chromatographic analytical approaches for quantification. This review aims to present these new developments in laser-based methods for the analysis of low-molecular weight compounds by MS and several potential applications. Copyright © 2016 Elsevier Inc. All rights reserved.

High Surface Area of Porous Silicon Drives Desorption of Intact Molecules

PubMed Central

Northen, Trent R.; Woo, Hin-Koon; Northen, Michael T.; Nordström, Anders; Uritboonthail, Winnie; Turner, Kimberly L.; Siuzdak, Gary

2007-01-01

The surface structure of porous silicon used in desorption/ionization on porous silicon (DIOS) mass analysis is known to play a primary role in the desorption/ionization (D/I) process. In this study, mass spectrometry and scanning electron microscopy (SEM) are used to examine the correlation between intact ion generation with surface ablation, and surface morphology. The DIOS process is found to be highly laser energy dependent and correlates directly with the appearance of surface ions (Sin+ and OSiH+). A threshold laser energy for DIOS is observed (10 mJ/cm2), which supports that DIOS is driven by surface restructuring and is not a strictly thermal process. In addition, three DIOS regimes are observed which correspond to surface restructuring and melting. These results suggest that higher surface area silicon substrates may enhance DIOS performance. A recent example which fits into this mechanism is silicon nanowires surface which have a high surface energy and concomitantly requires lower laser energy for analyte desorpton. PMID:17881245

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

PubMed

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

2015-12-01

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

A combined application of thermal desorber and gas chromatography to the analysis of gaseous carbonyls with the aid of two internal standards.

PubMed

Kim, Ki-Hyun; Anthwal, A; Pandey, Sudhir Kumar; Kabir, Ehsanul; Sohn, Jong Ryeul

2010-11-01

In this study, a series of GC calibration experiments were conducted to examine the feasibility of the thermal desorption approach for the quantification of five carbonyl compounds (acetaldehyde, propionaldehyde, butyraldehyde, isovaleraldehyde, and valeraldehyde) in conjunction with two internal standard compounds. The gaseous working standards of carbonyls were calibrated with the aid of thermal desorption as a function of standard concentration and of loading volume. The detection properties were then compared against two types of external calibration data sets derived by fixed standard volume and fixed standard concentration approach. According to this comparison, the fixed standard volume-based calibration of carbonyls should be more sensitive and reliable than its fixed standard concentration counterpart. Moreover, the use of internal standard can improve the analytical reliability of aromatics and some carbonyls to a considerable extent. Our preliminary test on real samples, however, indicates that the performance of internal calibration, when tested using samples of varying dilution ranges, can be moderately different from that derivable from standard gases. It thus suggests that the reliability of calibration approaches should be examined carefully with the considerations on the interactive relationships between the compound-specific properties and the operation conditions of the instrumental setups.

Gas emission from the UO2 samples, containing fission products and burnable absorber

NASA Astrophysics Data System (ADS)

Kopytin, V. P.; Baranov, V. G.; Burlakova, M. A.; Tenishev, A. V.; Kuzmin, R. S.; Pokrovskiy, S. A.; Mikhalchik, V. V.

2016-04-01

The process gas released from the fuel pellets of uranium fuel during fuel burn-up reduces the thermal conductivity of the rod-shell gap, enhances hydrogen embrittlement of the cladding material, causes it's carbonization, as well as transport processes in the fuel. In this study a technique of investigating the thermal desorption of gases from the UO2 fuel material were perfected in the temperature range 300-2000 K for uniform sample heating rate of 15 K/min in vacuum. The characteristic kinetic dependences are acquired for the gas emission from UO2 samples, containing simulators of fission products (SFP) and the burnable neutron absorber (BNA). Depending on the amount of SFP and BNA contained in the sample thermal desorption gas spectra (TDGS) vary. The composition of emitted gas varies, as well as the number of peaks in the TDGS and the peaks shift to higher temperatures. This indicates that introduction of SFPs and BNA alters the sample material structure and cause the creation of so- called traps which have different bonding energies to the gases. The traps can be a grid of dislocations, voids, and contained in the UO2 matrix SFP and BNA. Similar processes will occur in the fuel pellets in the real conditions of the Nuclear Power Plant as well.

Annealing effect on thermodynamic and physical properties of mesoporous silicon: A simulation and nitrogen sorption study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, Pushpendra, E-mail: pkumar-iitd@yahoo.com; Huber, Patrick, E-mail: patrick.huber@tuhh.de

Discovery of porous silicon formation in silicon substrate in 1956 while electro-polishing crystalline Si in hydrofluoric acid (HF), has triggered large scale investigations of porous silicon formation and their changes in physical and chemical properties with thermal and chemical treatment. A nitrogen sorption study is used to investigate the effect of thermal annealing on electrochemically etched mesoporous silicon (PS). The PS was thermally annealed from 200°C to 800°C for 1 hr in the presence of air. It was shown that the pore diameter and porosity of PS vary with annealing temperature. The experimentally obtained adsorption / desorption isotherms show hysteresis typicalmore » for capillary condensation in porous materials. A simulation study based on Saam and Cole model was performed and compared with experimentally observed sorption isotherms to study the physics behind of hysteresis formation. We discuss the shape of the hysteresis loops in the framework of the morphology of the layers. The different behavior of adsorption and desorption of nitrogen in PS with pore diameter was discussed in terms of concave menisci formation inside the pore space, which was shown to related with the induced pressure in varying the pore diameter from 7.2 nm to 3.4 nm.« less

Infrared Spectra and Binding Energies of Chemical Warfare Nerve Agent Simulants on the Surface of Amorphous Silica

DTIC Science & Technology

2013-06-24

Limited TPD of Water from Zeolite Linde 4A. Thermochim. Acta 1998, 319 (1), 177−184. (43) Palermo, A.; Löffler, D. G. Kinetics of Water Desorption...from Pelletized 4A and 5A Zeolites . Thermochim. Acta 1990, 159, 171−176. (44) Gorte, R. J. Design Parameters for Temperature Programmed Desorption from

Thermal induced BCN nanosheets evolution and its usage as metal-free catalyst in ethylbenzene dehydrogenation

NASA Astrophysics Data System (ADS)

Wang, Liancheng; Wang, Conghui; Zhang, Zhenwei; Wu, Jianghong; Ding, Ruimin; Lv, Baoliang

2017-11-01

Compared with mushroomed progress in metal-free C-rich BCN catalysts, little is known about the BN-rich BCN or even BN ones. Its related study has drawn great interest recently but still in its infancy stage. In this study, three kinds of BCN nanosheets (NSs) with tuned surface carbon contents (5.5-14.3%), specific surface area (SSA, 82-290 m2/g) and morphologies (ultrathin nanosheets, triangular plates) were fabricated through a solid state reaction by simply adjusting the reaction temperature, and those effects on the ethylbenzene dehydrogenation performances were studied in CO2 atmosphere. The morphology evolution of BCN NSs from ultrathin nanosheets to the triangular plates was observed and control experiments were carried out. The BCN nanosheets show relatively strong interaction with CO2 and distinct CO2 absorption properties. The CO2 temperature programmed desorption also indicates that the desorption peaks of CO2 are above 400 °C, enabling them potential CO2 utilization catalysts. A weak association was found between the surface C contents and the catalytic performance as it normalized with SSA, and the B-O species could be taken as an active site in CO2 atmosphere. Though much progress still needed, it is convincing that the BCN catalyst could be a promising metal-free catalyst in dehydrogenation beyond carbocatalyst.

Photothermal Desorption of Single-Walled Carbon Nanotubes and Coconut Shell-Activated Carbons Using a Continuous Light Source for Application in Air Sampling

PubMed Central

Floyd, Evan L.; Sapag, Karim; Oh, Jonghwa; Lungu, Claudiu T.

2014-01-01

Many techniques exist to measure airborne volatile organic compounds (VOCs), each with differing advantages; sorbent sampling is compact, versatile, has good sample stability, and is the preferred technique for collecting VOCs for hygienists. Development of a desorption technique that allows multiple analyses per sample (similar to chemical desorption) with enhanced sensitivity (similar to thermal desorption) would be helpful to field hygienists. In this study, activated carbon (AC) and single-walled carbon nanotubes (SWNT) were preloaded with toluene vapor and partially desorbed with light using a common 12-V DC, 50-W incandescent/halogen lamp. A series of experimental chamber configurations were explored starting with a 500-ml chamber under static conditions, then with low ventilation and high ventilation, finally a 75-ml high ventilation chamber was evaluated. When preloaded with toluene and irradiated at the highest lamp setting for 4min, AC desorbed 13.9, 18.5, 23.8, and 45.9% of the loaded VOC mass, in each chamber configuration, respectively; SWNT desorbed 25.2, 24.3, 37.4, and 70.5% of the loaded VOC mass, respectively. SWNT desorption was significantly greater than AC in all test conditions (P = 0.02–<0.0001) demonstrating a substantial difference in sorbent performance. When loaded with 0.435mg toluene and desorbed at the highest lamp setting for 4min in the final chamber design, the mean desorption for AC was 45.8% (39.7, 52.0) and SWNT was 72.6% (68.8, 76.4) (mean represented in terms of 95% confidence interval). All desorption measurements were obtained using a field grade photoionization detector; this demonstrates the potential of using this technique to perform infield prescreening of VOC samples for immediate exposure feedback and in the analytical lab to introduce sample to a gas chromatograph for detailed analysis of the sample. PMID:25016598

Photothermal desorption of single-walled carbon nanotubes and coconut shell-activated carbons using a continuous light source for application in air sampling.

PubMed

Floyd, Evan L; Sapag, Karim; Oh, Jonghwa; Lungu, Claudiu T

2014-08-01

Many techniques exist to measure airborne volatile organic compounds (VOCs), each with differing advantages; sorbent sampling is compact, versatile, has good sample stability, and is the preferred technique for collecting VOCs for hygienists. Development of a desorption technique that allows multiple analyses per sample (similar to chemical desorption) with enhanced sensitivity (similar to thermal desorption) would be helpful to field hygienists. In this study, activated carbon (AC) and single-walled carbon nanotubes (SWNT) were preloaded with toluene vapor and partially desorbed with light using a common 12-V DC, 50-W incandescent/halogen lamp. A series of experimental chamber configurations were explored starting with a 500-ml chamber under static conditions, then with low ventilation and high ventilation, finally a 75-ml high ventilation chamber was evaluated. When preloaded with toluene and irradiated at the highest lamp setting for 4min, AC desorbed 13.9, 18.5, 23.8, and 45.9% of the loaded VOC mass, in each chamber configuration, respectively; SWNT desorbed 25.2, 24.3, 37.4, and 70.5% of the loaded VOC mass, respectively. SWNT desorption was significantly greater than AC in all test conditions (P = 0.02-<0.0001) demonstrating a substantial difference in sorbent performance. When loaded with 0.435mg toluene and desorbed at the highest lamp setting for 4min in the final chamber design, the mean desorption for AC was 45.8% (39.7, 52.0) and SWNT was 72.6% (68.8, 76.4) (mean represented in terms of 95% confidence interval). All desorption measurements were obtained using a field grade photoionization detector; this demonstrates the potential of using this technique to perform infield prescreening of VOC samples for immediate exposure feedback and in the analytical lab to introduce sample to a gas chromatograph for detailed analysis of the sample. © The Author 2014. Published by Oxford University Press on behalf of the British Occupational Hygiene Society.

Electron- and Photon-stimulated Desorption of Alkali Atoms from Lunar Sample and a Model Mineral Surface

NASA Technical Reports Server (NTRS)

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

2003-01-01

We report recent results on an investigation of source mechanisms for the origin of alkali atoms in the tenuous planetary atmospheres, with focus on non-thermal processes (photon stimulated desorption (PSD), electron stimulated desorption (ESD), and ion sputtering). Whereas alkaline earth oxides (MgO, CaO) are far more abundant in lunar samples than alkali oxides (Na2O, K2O), the atmosphere of the Moon contains easily measurable concentrations of Na and K, while Ca and Mg are undetected there; traces of Ca have recently been seen in the Moon's atmosphere (10-3 of Na). The experiments have included ESD, PSD and ion sputtering of alkali atoms from model mineral surface (amorphous SiO2) and from a lunar basalt sample obtained from NASA. The comparison is made between ESD and PSD efficiency of monovalent alkalis (Na, K) and divalent alkaline earths (Ba, Ca).The ultrahigh vacuum measurement scheme for ESD and PSD of Na atoms includes a highly sensitive alkali metal detector based on surface ionization, and a time-of-flight technique. For PSD measurements, a mercury arc light source (filtered and chopped) is used. We find that bombardment of the alkali covered surfaces by ultraviolet photons or by low energy electrons (E>4 eV) causes desorption of hot alkali atoms. This results are consistent with the model developed to explain our previous measurements of sodium desorption from a silica surface and from water ice: electron- or photon-induced charge transfer from the substrate to the ionic adsorbate causes formation of a neutral alkali atom in a repulsive configuration, from which desorption occurs. The two-electron charge transfer to cause desorption of divalent alkaline eath ions is a less likely process.The data support the suggestion that PSD by UV solar photons is a dominant source process for alkalis in the tenuous lunar atmosphere.

FOREWORD: The 12th International Workshop on Desorption Induced by Electronic Transitions (DIET XII) (Pine Mountain, Georgia, USA, 19-23 April 2009) The 12th International Workshop on Desorption Induced by Electronic Transitions (DIET XII) (Pine Mountain, Georgia, USA, 19-23 April 2009)

NASA Astrophysics Data System (ADS)

Orlando, Thomas M.; Diebold, Ulrike

2010-03-01

The 12th International Workshop on Desorption Induced by Electronic Transitions (DIET XII) took place from 19-23 April 2009 in Pine Mountain, Georgia, USA. This was the 12th conference in a strong and vibrant series, which dates back to the early 1980s. DIET XII continued the tradition of exceptional interdisciplinary science and focused on the study of desorption and dynamics induced by electronic excitations of surfaces and interfaces. The format involved invited lectures, contributed talks and a poster session on the most recent developments and advances in this area of surface physics. The Workshop International Steering Committee and attendees wish to dedicate DIET XII to the memory of the late Professor Theodore (Ted) Madey. Ted was one of the main pioneers of this field and was one of the primary individuals working to keep this area of science exciting and adventurous. His overall contributions to surface science were countless and his contributions to the DIET field and community were enormous. He is missed and remembered by many friends and colleagues throughout the world. The papers collected in this issue cover many of the highlights of DIET XII. Topics include ultrafast electron transfer at surfaces and interfaces, quantum and spatially resolved mapping of surface dynamics and desorption, photon-, electron- and ion-beam induced processes at complex interfaces, the role of non-thermal desorption in astrochemistry and astrophysics and laser-/ion-based methods of examining soft matter and biological media. Although the workshop attracted many scientists active in the general area of non-thermal surface processes, DIET XII also attracted many younger scientists (i.e., postdoctoral fellows, advanced graduate students, and a select number of advanced undergraduate students). This field has had an impact in a number of areas including nanoscience, device physics, astrophysics, and now biophysics. We believe that this special issue of Journal of Physics: Condensed Matter will help foster further progress in the study of DIET processes. Since the field remains vibrant and exciting, the workshop series will continue with DIET XIII. Professor Richard Palmer (University of Birmingham, UK) will chair DIET XIII in the UK in early summer 2012. We gratefully acknowledge financial support from SPECS, HIDEN Analytical, BRUKER, The United States National Science Foundation, Georgia Institute of Technology and The State University of New Jersey, Rutgers.

The anodic emitter effect and its inversion demonstrated by temperature measurements at doped and undoped tungsten electrodes

NASA Astrophysics Data System (ADS)

Hoebing, T.; Bergner, A.; Hermanns, P.; Mentel, J.; Awakowicz, P.

2016-04-01

The admixture of a small amount of emitter oxides, e.g. \\text{Th}{{\\text{O}}2} , \\text{L}{{\\text{a}}2}{{\\text{O}}3} or \\text{C}{{\\text{e}}2}{{\\text{O}}3} to tungsten generates the so-called emitter effect. It reduces the work function of tungsten cathodes, that are applied in high intensity discharge (HID) lamps. After leaving the electrode bulk and moving to the surface, a monolayer of Th, La, or Ce atoms is formed on the surface, which reduces the effective work function ϕ. Depending on the coverage of the electrode, the effective reduction in ϕ is subjected to the thermal desorption of the monolayer from the hot electrode surface. The thermal desorption of emitter atoms from the cathode is compensated not only by the supply from the interior of the electrode and by surface diffusion of the emitter material to its tip, but also to a large extent by a repatriation of the emitter ions from the plasma by the strong electric field in front of the cathode. Yet, an emitter ion current from the arc discharge to the anode may only be present, if the anode is cold enough to refrain from thermionic emission. Therefore, the ability of emitter oxides to reduce the temperature of tungsten anodes is only given for a moderate temperature so that the thermal desorption is low and an additional ion current is present in front of the anode. A higher electrode temperature leads to their evaporation and to an inversion of the emitter effect, which increases the temperature of the respective anodes in comparison with pure tungsten anodes. Within this article, the emitter effect of doped tungsten anodes and the transition to its inversion is investigated for thoriated, lanthanated, and ceriated tungsten electrodes by measurements of the electrode temperature in dependence on the discharge current. It is shown for a lanthanated and a ceriated anode that the emitter effect is sustained by an ion current at anode temperatures at which the thermal evaporation of emitter material is completed.

Bulk and molecular-level characterization of laboratory-aged biomass burning organic aerosol from oak leaf and heartwood fuels

NASA Astrophysics Data System (ADS)

Fortenberry, Claire F.; Walker, Michael J.; Zhang, Yaping; Mitroo, Dhruv; Brune, William H.; Williams, Brent J.

2018-02-01

The chemical complexity of biomass burning organic aerosol (BBOA) greatly increases with photochemical aging in the atmosphere, necessitating controlled laboratory studies to inform field observations. In these experiments, BBOA from American white oak (Quercus alba) leaf and heartwood samples was generated in a custom-built emissions and combustion chamber and photochemically aged in a potential aerosol mass (PAM) flow reactor. A thermal desorption aerosol gas chromatograph (TAG) was used in parallel with a high-resolution time-of-flight aerosol mass spectrometer (AMS) to analyze BBOA chemical composition at different levels of photochemical aging. Individual compounds were identified and integrated to obtain relative decay rates for key molecules. A recently developed chromatogram binning positive matrix factorization (PMF) technique was used to obtain mass spectral profiles for factors in TAG BBOA chromatograms, improving analysis efficiency and providing a more complete determination of unresolved complex mixture (UCM) components. Additionally, the recently characterized TAG decomposition window was used to track molecular fragments created by the decomposition of thermally labile BBOA during sample desorption. We demonstrate that although most primary (freshly emitted) BBOA compounds deplete with photochemical aging, certain components eluting within the TAG thermal decomposition window are instead enhanced. Specifically, the increasing trend in the decomposition m/z 44 signal (CO2+) indicates formation of secondary organic aerosol (SOA) in the PAM reactor. Sources of m/z 60 (C2H4O2+), typically attributed to freshly emitted BBOA in AMS field measurements, were also investigated. From the TAG chemical speciation and decomposition window data, we observed a decrease in m/z 60 with photochemical aging due to the decay of anhydrosugars (including levoglucosan) and other compounds, as well as an increase in m/z 60 due to the formation of thermally labile organic acids within the PAM reactor, which decompose during TAG sample desorption. When aging both types of BBOA (leaf and heartwood), the AMS data exhibit a combination of these two contributing effects, causing limited change to the overall m/z 60 signal. Our observations demonstrate the importance of chemically speciated data in fully understanding bulk aerosol measurements provided by the AMS in both laboratory and field studies.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

1997-04-01

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

Comparison of Adsorption/Desorption of Volatile Organic Compounds (VOCs) on Electrospun Nanofibers with Tenax TA for Potential Application in Sampling

PubMed Central

Chu, Lanling; Deng, Siwei; Zhao, Renshan; Deng, Jianjun; Kang, Xuejun

2016-01-01

The objective of this study was to compare the adsorption/desorption of target compounds on homemade electrospun nanofibers, polystyrene (PS) nanofibers, acrylic resin (AR) nanofibers and PS-AR composite nanofibers with Tenax TA. Ten volatile organic compounds (VOCs) were analyzed by preconcentration onto different sorbents followed by desorption (thermal and solvent orderly) and analysis by capillary gas chromatography. In comparison to Tenax TA, the electrospun nanofibers displayed a significant advantage in desorption efficiency and adsorption selectivity. Stability studies were conducted as a comparative experiment between PS-AR nanofibers and Tenax TA using toluene as the model compound. No stability problems were observed upon storage of toluene on both PS-AR nanofibers and Tenax TA over 60 hours period when maintained in an ultra-freezer (−80°C). The nanofibers provided slightly better stability for the adsorbed analytes than Tenax TA under other storage conditions. In addition, the nanofibers also provided slightly better precision than Tenax TA. The quantitative adsorption of PS-AR nanofibers exhibited a good linearity, as evidenced by the 0.988–0.999 range of regression coefficients (R). These results suggest that for VOCs sampling the electrospun nanofibers can be a potential ideal adsorbent. PMID:27776140

Astrochem: Abundances of chemical species in the interstellar medium

NASA Astrophysics Data System (ADS)

Maret, Sébastien; Bergin, Edwin A.

2015-07-01

Astrochem computes the abundances of chemical species in the interstellar medium, as function of time. It studies the chemistry in a variety of astronomical objects, including diffuse clouds, dense clouds, photodissociation regions, prestellar cores, protostars, and protostellar disks. Astrochem reads a network of chemical reactions from a text file, builds up a system of kinetic rates equations, and solves it using a state-of-the-art stiff ordinary differential equation (ODE) solver. The Jacobian matrix of the system is computed implicitly, so the resolution of the system is extremely fast: large networks containing several thousands of reactions are usually solved in a few seconds. A variety of gas phase process are considered, as well as simple gas-grain interactions, such as the freeze-out and the desorption via several mechanisms (thermal desorption, cosmic-ray desorption and photo-desorption). The computed abundances are written in a HDF5 file, and can be plotted in different ways with the tools provided with Astrochem. Chemical reactions and their rates are written in a format which is meant to be easy to read and to edit. A tool to convert the chemical networks from the OSU and KIDA databases into this format is also provided. Astrochem is written in C, and its source code is distributed under the terms of the GNU General Public License (GPL).

Deuterium desorption from ion-irradiated tantalum and effects on surface morphology

NASA Astrophysics Data System (ADS)

Novakowski, T. J.; Sundaram, A.; Tripathi, J. K.; Gonderman, S.; Hassanein, A.

2018-06-01

Compared to tungsten (W), tantalum (Ta) has shown superior resistance to helium (He)-induced surface morphology changes under fusion-relevant irradiation conditions. However, Ta is also expected to have a stronger interaction with hydrogen isotopes, potentially limiting its use as a plasma-facing material. Despite these concerns, detailed investigations on hydrogen irradiation effects on Ta are scarce. In this study, pristine and fuzzy (He+ ion-irradiated) Ta samples are irradiated with 120 eV deuterium (D) ions at various temperatures and examined with a combination of thermal desorption spectroscopy (TDS), scanning electron microscopy (SEM), and optical reflectivity. TDS reveals discrete D desorption temperatures at 660 and 760 K, corresponding to trapping energies of 1.82 and 2.11 eV, respectively. Although D is retained in Ta both in higher quantities and at higher temperatures compared to W, extreme surface temperatures expected in tokamak divertors may exceed these desorption temperatures and counteract retention. Furthermore, this study indicates that Ta is relatively resistant to adverse surface structuring under D+ ion irradiation. In fact, D+ is shown to prevent and suppress Ta fuzz formation in sequential D+/He+ ion irradiation experiments. While further investigations are needed to elucidate this behavior, these initial investigations show a strong potential for the use of Ta as a PFC material.

Correlation between oxygen stoichiometry, structure, and opto-electrical properties in amorphous In2O3:H films

NASA Astrophysics Data System (ADS)

Koida, Takashi; Shibata, Hajime; Kondo, Michio; Tsutsumi, Koichi; Sakaguchi, Akio; Suzuki, Michio; Fujiwara, Hiroyuki

2012-03-01

We have characterized amorphous In2O3:H (H : ˜4 at.%) transparent conducting films by Rutherford backscattering spectrometry (RBS), thermal desorption spectroscopy, spectroscopic ellipsometry, and Hall measurements. The amorphous In2O3:H films have been fabricated at room temperature by sputtering of an In2O3 ceramic target under Ar, O2, and H2O vapor with variation of a flow ratio r(O2) = O2/(O2+Ar). We observe (i) signals originating from Ar in RBS spectra for all the films and (ii) desorption of H2O and Ar gases during post thermal annealing of the films. Furthermore, O2 desorption together with H2O and Ar is observed for the films grown at r(O2) > 0.375%, whereas In desorption together with H2O and Ar is observed for the films grown at r(O2) < 0.375%. These results suggest that the films have void and/or multi-vacancy rich structures inside the amorphous network, and the variety of atoms, such as Ar, H2O, and weakly bonded O and In, is present in the void structures for the films grown at O2-rich and O2-poor conditions, respectively. Corresponding to the structural changes, optical and electrical properties also change at r(O2) = 0.375%. For the films grown at r(O2) < 0.375%, we observe a broad absorption in the visible wavelengths that cannot be explained by free carrier absorption. In this film, the carrier mobility reduces rapidly with increasing carrier density. Analysis of spectroscopic ellipsometry and Hall measurements reveals that a large decrease in mobility is due to a large increase in carrier effective mass, in addition to the effect of ionized impurity scattering. In this article, we discuss the optical and transport properties with the variation of oxygen stoichiometry and microscopic structures in the amorphous In2O3:H films.

Effect of Vaporizer Temperature on Ambient Non-Refractory Submicron Aerosol Composition and Mass Spectra Measured by the Aerosol Mass Spectrometer

EPA Science Inventory

Aerodyne Aerosol Mass Spectrometers (AMS) are routinely operated with a constant vaporizer temperature (Tvap) of 600^oC in order to facilitate quantitative detection of non-refractory submicron (NR-PM1) species. By analogy with other thermal desorption instrument...

CLEANING UP PESTICIDE CONTAMINATED SOILS: COMPARING EFFECTIVENESS OF SUPERCRITICAL FLUID EXTRACTION WITH SOLVENT EXTRACTION AND LOW TEMPERATURE THERMAL DESORPTION

EPA Science Inventory

Bench-scale supercritical fluid extraction (SFE) studies were performed on soil samples obtained from a Superfund site that is contaminated with high levels of p,p,-DDT, p,p,-DDD, p,p,-DDE, toxaphene and hexachlorocyclohexane. The effectiveness of supercritical fluid extraction ...

24-HOUR DIFFUSIVE SAMPLING OF TOXIC VOCS IN AIR ONTO CARBOPACK X SOLID ADSORBENT FOLLOWED BY THERMAL DESORPTION/GC/MS ANALYSIS - LABORATORY STUDIES

EPA Science Inventory

Diffusive sampling of a mixture of 42 volatile organic compounds (VOCs) in humidified, purified air onto the solid adsorbent Carbopack X was evaluated under controlled laboratory conditions. The evaluation included variations in sample air temperature, relative humidity, and ozon...

Effect of Nb on Delayed Fracture Resistance of Ultra-High Strength Martensitic Steels

NASA Astrophysics Data System (ADS)

Song, Rongjie; Fonstein, Nina; Pottore, Narayan; Jun, Hyun Jo; Bhattacharya, Debanshu; Jansto, Steve

Ultra-high strength steels are materials of considerable interest for automotive and structural applications and are increasingly being used in those areas. Higher strength, however, makes steels more prone to hydrogen embrittlement (HE). The effects of Nb and other alloying elements on the hydrogen-induced delayed fracture resistance of cold rolled martensitic steels with ultra-high strength 2000 MPa were studied using an acid immersion test, thermal desorption analysis (TDA) and measuring of permeation. The microstructure was characterized by high resolution field emission Scanning Electron Microscopy (SEM) with Electron Backscattered Diffraction (EBSD) and Transmission Electron Microscopy (TEM). It was shown that the combined addition of Nb significantly improved the delayed fracture resistance of investigated steel. The addition of Nb to alloyed martensitic steels resulted in very apparent grain refinement of the prior austenite grain size. The Nb microalloyed steel contained a lower diffusible hydrogen content during thermal desorption analysis as compared to the base steel and had a higher trapped hydrogen amount after charging. The reason that Nb improved the delayed fracture resistance of steels can be attributed mostly to both hydrogen trapping and grain refinement.

Development and validation of a sensitive thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) method for the determination of phosgene in air samples.

PubMed

Juillet, Y; Dubois, C; Bintein, F; Dissard, J; Bossée, A

2014-08-01

A new rapid, sensitive and reliable method was developed for the determination of phosgene in air samples using thermal desorption (TD) followed by gas chromatography-mass spectrometry (GC-MS). The method is based on a fast (10 min) active sampling of only 1 L of air onto a Tenax® GR tube doped with 0.5 mL of derivatizing mixture containing dimercaptotoluene and triethylamine in hexane solution. Validation of the TD-GC-MS method showed a low limit of detection (40 ppbv), acceptable repeatability, intermediate fidelity (relative standard deviation within 12 %) and excellent accuracy (>95%). Linearity was demonstrated for two concentration ranges (0.04 to 2.5 ppmv and 2.5 to 10 ppmv) owing to variation of derivatization recovery between low and high concentration levels. Due to its simple on-site implementation and its close similarity with recommended operating procedure (ROP) for chemical warfare agents vapour sampling, the method is particularly useful in the process of verification of the Chemical Weapons Convention.

Development and evaluation of a silver mordenite composite sorbent for the partitioning of xenon from krypton in gas compositions

DOE PAGES

Garn, Troy G.; Greenhalgh, Mitchell; Law, Jack D.

2015-12-22

A new engineered form composite sorbent for the selective separation of xenon from krypton in simulant composition off-gas streams resulting from the reprocessing of used nuclear fuel has been developed and evaluated. A sodium mordenite powder was incorporated into a macroporous polymer binder, formed into spherical beads and successfully converted to a 9 wt.% silver form composite sorbent. The final engineered form sorbent retained the characteristic surface area indicative of sodium mordenite powder. The sorbent was evaluated for xenon adsorption potential with capacities measured as high as 30 millimoles of xenon per kilogram of sorbent achieved at ambient temperature andmore » 460 millimoles of xenon per kilogram sorbent at 220 K. Xenon/krypton selectivity was calculated to be 22.4 with a 1020 µL/L xenon, 150 µL/L krypton in a balance of air feed gas at 220 K. Furthermore, adsorption/desorption thermal cycling effects were evaluated with results indicating sorbent performance was not significantly impacted while undergoing numerous adsorption/desorption thermal cycles.« less

Superfund record of decision (EPA Region 4): T H Agriculture and Nutrition Site, Dougherty County, Albany, GA, April 26, 1996

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

This decision document (Record of Decision), presents the selected Remedial Action for the Operable Unit Two for the T H Agriculture & Nutrition (THAN) Site, Albany, Georgia. The second operable unit addresses the source of the contamination on the eastern parcel of the Site. The major components of the selected remedy for operable unit two include: the excavation of all soil contaminated with organics necessary to meet performance standards; the staging and preconditioning of soil for low temperature thermal desorption treatment; the treatment of excavated soil by low temperature thermal desorption; the placement of treated, decontaminated soil back to themore » site; periodic sampling of treated soil during the treatment process to verify the effectiveness of the remedy; air monitoring to ensure safety of nearby residents and workers; groundwater monitoring to ensure that metals contaminated remaining in the subsurface soil will not result in contaminated groundwater migrating offsite in concentrations which exceed groundwater protection standards; and deed restrictions to prevent residential use of the property.« less

A star-shaped polythiophene dendrimer coating for solid-phase microextraction of triazole agrochemicals.

PubMed

Abolghasemi, Mir Mahdi; Habibiyan, Rahim; Jaymand, Mehdi; Piryaei, Marzieh

2018-02-14

A nanostructured star-shaped polythiophene dendrimer was prepared and used as a fiber coating for headspace solid phase microextraction of selected triazolic pesticides (tebuconazole, hexaconazole, penconazole, diniconazole, difenoconazole, triticonazole) from water samples. The dendrimer with its large surface area was characterized by thermogravimetric analysis, UV-Vis spectroscopy and field emission scanning electron microscopy. It was placed on a stainless steel wire for use in SPME. The experimental conditions for fiber coating, extraction, stirring rate, ionic strength, pH value, desorption temperature and time were optimized. Following thermal desorption, the pesticides were quantified by GC-MS. Under optimum conditions, the repeatability (RSD) for one fiber (for n = 3) ranges from 4.3 to 5.6%. The detection limits are between 8 and 12 pg mL -1 . The method is fast, inexpensive (in terms of equipment), and the fiber has high thermal stability. Graphical abstract Schematic presentation of a nanostructured star-shaped polythiophene dendrimer for use in headspace solid phase microextraction of the triazolic pesticides (tebuconazole, hexaconazole, penconazole, diniconazole, difenoconazole, triticonazole). They were then quantified by gas chromatography-mass spectrometry.

Rapid screening of basic colorants in processed vegetables through mass spectrometry using an interchangeable thermal desorption electrospray ionization source.

PubMed

Chao, Yu-Ying; Chen, Yen-Ling; Lin, Hong-Yi; Huang, Yeou-Lih

2018-06-20

Thermal desorption electrospray ionization/mass spectrometry (TD-ESI-MS) employing a quickly interchangeable ionization source is a relatively new ambient ionization mass spectrometric technique that has had, to date, only a limited number of applications related to food safety control. With reallocation of resources, this direct-analysis technique has had wider use in food analysis when operated in dual-working mode (pretreatment-free qualitative screening and conventional quantitative confirmation) after switching to an ambient ionization source from a traditional atmospheric pressure ionization source. Herein, we describe the benefits and challenges associated with the use of a TD-ESI source to detect adulterants in processed vegetables (PVs), as a proof-of-concept for the detection of basic colorants. While TD-ESI can offer direct qualitative screening analyses for PVs with detection capabilities lower than those provided with liquid chromatography/UV detection within 30 s, the use of TD-ESI for semi-quantification is applicable only for homogeneous food matrices. Copyright © 2018 Elsevier B.V. All rights reserved.

Rapid detection of illegal colorants on traditional Chinese pastries through mass spectrometry with an interchangeable thermal desorption electrospray ionization source.

PubMed

Chao, Yu-Ying; Chen, Yen-Ling; Chen, Wei-Chu; Chen, Bai-Hsiun; Huang, Yeou-Lih

2018-06-30

Ambient mass spectrometry using an interchangeable thermal desorption/electrospray ionization source (TD-ESI) is a relatively new technique that has had only a limited number of applications to date. Nevertheless, this direct-analysis technique has potential for wider use in analytical chemistry (e.g., in the rapid direct detection of contaminants, residues, and adulterants on and in food) when operated in dual-working mode (pretreatment-free qualitative screening and conventional quantitative confirmation) after switching to a TD-ESI source from a conventional ESI source. Herein, we describe the benefits and challenges associated with the use of a TD-ESI source to detect adulterants on traditional Chinese pastries (TCPs), as a proof-of-concept for the detection of illegal colorants. While TD-ESI can offer direct (i.e., without any sample preparation) qualitative screening analyses for TCPs with adequate sensitivity within 30 s, the use of TD-ESI for semi-quantification is applicable only for homogeneous matrices (e.g., tang yuan). Copyright © 2017 Elsevier Ltd. All rights reserved.

Effects of alloying elements on thermal desorption of helium in Ni alloys

NASA Astrophysics Data System (ADS)

Xu, Q.; Cao, X. Z.; Sato, K.; Yoshiie, T.

2012-12-01

It is well known that the minor elements Si and Sn can suppress the formation of voids in Ni alloys. In the present study, to investigate the effects of Si and Sn on the retention of helium in Ni alloys, Ni, Ni-Si, and Ni-Sn alloys were irradiated by 5 keV He ions at 723 K. Thermal desorption spectroscopy (TDS) was performed at up to 1520 K, and microstructural observations were carried out to identify the helium trapping sites during the TDS analysis. Two peaks, at 1350 and 1457 K, appeared in the TDS spectrum of Ni. On the basis of the microstructural observations, the former peak was attributed to the release of trapped helium from small cavities and the latter to its release from large cavities. Small-cavity helium trapping sites were also found in the Ni-Si and Ni-Sn alloys, but no large cavities were observed in these alloys. In addition, it was found that the oversized element Sn could trap He atoms in the Ni-Sn alloy.

Comprehensive evaluation of direct injection mass spectrometry for the quantitative profiling of volatiles in food samples

PubMed Central

2016-01-01

Although qualitative strategies based on direct injection mass spectrometry (DIMS) have recently emerged as an alternative for the rapid classification of food samples, the potential of these approaches in quantitative tasks has scarcely been addressed to date. In this paper, the applicability of different multivariate regression procedures to data collected by DIMS from simulated mixtures has been evaluated. The most relevant factors affecting quantitation, such as random noise, the number of calibration samples, type of validation, mixture complexity and similarity of mass spectra, were also considered and comprehensively discussed. Based on the conclusions drawn from simulated data, and as an example of application, experimental mass spectral fingerprints collected by direct thermal desorption coupled to mass spectrometry were used for the quantitation of major volatiles in Thymus zygis subsp. zygis chemotypes. The results obtained, validated with the direct thermal desorption coupled to gas chromatography–mass spectrometry method here used as a reference, show the potential of DIMS approaches for the fast and precise quantitative profiling of volatiles in foods. This article is part of the themed issue ‘Quantitative mass spectrometry’. PMID:27644978

Rotational state modification and fast ortho-para conversion of H2 trapped within the highly anisotropic potential of Pd(210)

NASA Astrophysics Data System (ADS)

Ohno, S.; Ivanov, D.; Ogura, S.; Wilde, M.; Arguelles, E. F.; Diño, W. A.; Kasai, H.; Fukutani, K.

2018-02-01

The rotational state and ortho-para conversion of H2 on a Pd(210) surface is investigated with rotational-state-selective temperature-programmed desorption (RS-TPD) and theoretical calculations. The isotope dependence of TPD shows a higher desorption energy for D2 than that for H2, which is ascribed to the rotational and zero-point vibrational energies. The RS-TPD data show that the desorption energy of H2(J =1 ) (J : rotational quantum number) is higher than that of H2(J =0 ). This is due to the orientationally anisotropic potential confining the adsorbed H2, which is in agreement with theoretical calculations. Furthermore, the H2 desorption intensity ratio in J =1 and J =0 indicates fast ortho-para conversion in the adsorption state, which we estimate to be of the order of 1 s.

Coadsorbed species explain the mechanism of methanol temperature-desorption on CeO 2(111)

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 CeO 2(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 themore » surface and react at higher temperatures to form methanol and formaldehyde by a disproportionation mechanism. Alternatively, the stabilized methoxy groups undergo sequential C–H scission reactions to produce formaldehyde. Calculated energy requirements and methanol/formaldehyde selectivity agree with the experimental data.« less

Adsorption, desorption, and displacement kinetics of H2O and CO2 on TiO2(110).

PubMed

Smith, R Scott; Li, Zhenjun; Chen, Long; Dohnálek, 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 (Ob), Ti5c, and defect sites in order of increasing peak temperature. Analysis of the saturated surface spectrum for both species reveals that the corresponding adsorption energies on all sites are greater for H2O than 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.

CCl 4 chemistry on the magnetite selvedge of single-crystal hematite: competitive surface reactions

NASA Astrophysics Data System (ADS)

Adib, K.; Camillone, N., III; Fitts, J. P.; Rim, K. T.; Flynn, G. W.; Joyce, S. A.; Osgood, R. M., Jr.

2002-01-01

Temperature programmed reaction/desorption (TPR/D) studies were undertaken to characterize the surface chemistry which occurs between CCl 4 and the Fe 3O 4 (1 1 1) selvedge of single crystal α-Fe 2O 3 (0 0 0 1). Six separate desorption events are clearly observed and four desorbing species are identified: CCl 4, OCCl 2, C 2Cl 4 and FeCl 2. It is proposed that OCCl 2, CCl 4 and C 2Cl 4 are produced in reactions involving the same precursor, CCl 2. Three reaction paths compete for the CCl 2 precursor: oxygen atom abstraction (for OCCl 2), molecular recombinative desorption (for CCl 4) and associative desorption (for C 2Cl 4). During the TPR/D temperature ramp, the branching ratio is observed to depend upon temperature and the availability of reactive sites. The data are consistent with a rich site-dependent chemistry.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Boseong; Dohnálek, Zdenek; Szanyi, János

2016-10-01

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 byproduct 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 product desorbs from TiO2(110)more » 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

Temperature-programmed desorption study of NO reactions on rutile TiO 2(110)-1×1

DOE PAGES

Kim, Boseong; Dohnalek, Zdenek; Szanyi, Janos; ...

2016-02-24

In this study, systematic temperature-programmed desorption (TPD) studies of NO adsorption and reactions on rutile TiO 2(110)-1 × 1 surface reveal several distinct reaction channels in a temperature range of 50–500 K. NO readily reacts on TiO 2(110) to form N 2O, which desorbs between 50 and 200 K (LT N 2O channels), which leaves the TiO 2 surface populated with adsorbed oxygen atoms (O a) as a by-product of N 2O formation. In addition, we observe simultaneous desorption peaks of NO and N 2O at 270 K (HT1 N 2O) and 400 K (HT2 N 2O), respectively, both ofmore » which are attributed to reaction-limited processes. No N-derived reaction product desorbs from TiO 2(110) surface above 500 K or higher, while the surface may be populated with Oa's and oxidized products such as NO 2 and NO 3. The adsorbate-free TiO 2 surface with oxygen vacancies can be regenerated by prolonged annealing at 850 K or higher. Detailed analysis of the three N 2O desorption yields reveals that the surface species for the HT channels are likely to be various forms of NO dimers.« less

Thermal decomposition in thermal desorption instruments: importance of thermogram measurements for analysis of secondary organic aerosol

NASA Astrophysics Data System (ADS)

Stark, H.; Yatavelli, R. L. N.; Thompson, S.; Kang, H.; Krechmer, J. E.; Kimmel, J.; Palm, B. B.; Hu, W.; Hayes, P.; Day, D. A.; Campuzano Jost, P.; Ye, P.; Canagaratna, M. R.; Jayne, J. T.; Worsnop, D. R.; Jimenez, J. L.

2017-12-01

Understanding the chemical composition of secondary organic aerosol (SOA) is crucial for explaining sources and fate of this important aerosol class in tropospheric chemistry. Further, determining SOA volatility is key in predicting its atmospheric lifetime and fate, due to partitioning from and to the gas phase. We present three analysis approaches to determine SOA volatility distributions from two field campaigns in areas with strong biogenic emissions, a Ponderosa pine forest in Colorado, USA, from the BEACHON-RoMBAS campaign, and a mixed forest in Alabama, USA, from the SOAS campaign. We used a high-resolution-time-of-flight chemical ionization mass spectrometer (CIMS) for both campaigns, equipped with a micro-orifice volatilization impactor (MOVI) inlet for BEACHON and a filter inlet for gases and aerosols (FIGAERO) for SOAS. These inlets allow near simultaneous analysis of particle and gas-phase species by the CIMS. While gas-phase species are directly measured without heating, particles undergo thermal desorption prior to analysis. Volatility distributions can be estimated in three ways: (1) analysis of the thermograms (signal vs. temperature); (2) via partitioning theory using the gas- and particle-phase measurements; (3) from measured chemical formulas via a group contribution model. Comparison of the SOA volatility distributions from the three methods shows large discrepancies for both campaigns. Results from the thermogram method are the most consistent of the methods when compared with independent AMS-thermal denuder measurements. The volatility distributions estimated from partitioning measurements are very narrow, likely due to signal-to-noise limits in the measurements. The discrepancy between the formula and the thermogram methods indicates large-scale thermal decomposition of the SOA species. We will also show results of citric acid thermal decomposition, where, in addition to the mass spectra, measurements of CO, CO2 and H2O were made, showing thermal decomposition of up to 65% of the citric acid molecules.

The Molecular Volcano Revisited: Determination of Crack Propagation and Distribution During the Crystallization of Nanoscale Amorphous Solid Water Films.

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

2012-02-02

Temperature programmed desorption (TPD) is utilized to determine the length distribution of cracks formed through amorphous solid water (ASW) during crystallization. This distribution is determined by monitoring how the thickness of an ASW overlayer alters desorption of an underlayer of O2. As deposited the ASW overlayer prevents desorption of O2. During crystallization, cracks form through the ASW overlayer and open a path to vacuum which allows O2 to escape in a rapid episodic release known as the 'molecular volcano'. Sufficiently thick ASW overlayers further trap O2 resulting in a second O2 desorption peak commensurate with desorption of the last ofmore » the ASW overlayer. The evolution of this trapping peak with overlayer thickness is the basis for determining the distribution of crystallization induced cracks through the ASW. Reflection adsorption infrared spectroscopy (RAIRS) and TPD of multicomponent parfait structures of ASW, O2 and Kr indicate that a preponderance of these cracks propagate down from the outer surface of the ASW.« less

Measurement of Passive Uptake Rates for Volatile Organic Compounds on Commercial Thermal Desorption Tubes and the Effect of Ozone on Sampling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maddalena, Randy; Parra, Amanda; Russell, Marion

Diffusive or passive sampling methods using commercially filled axial-sampling thermal desorption tubes are widely used for measuring volatile organic compounds (VOCs) in air. The passive sampling method provides a robust, cost effective way to measure air quality with time-averaged concentrations spanning up to a week or more. Sampling rates for VOCs can be calculated using tube geometry and Fick’s Law for ideal diffusion behavior or measured experimentally. There is evidence that uptake rates deviate from ideal and may not be constant over time. Therefore, experimentally measured sampling rates are preferred. In this project, a calibration chamber with a continuous stirredmore » tank reactor design and constant VOC source was combined with active sampling to generate a controlled dynamic calibration environment for passive samplers. The chamber air was augmented with a continuous source of 45 VOCs ranging from pentane to diethyl phthalate representing a variety of chemical classes and physiochemical properties. Both passive and active samples were collected on commercially filled Tenax TA thermal desorption tubes over an 11-day period and used to calculate passive sampling rates. A second experiment was designed to determine the impact of ozone on passive sampling by using the calibration chamber to passively load five terpenes on a set of Tenax tubes and then exposing the tubes to different ozone environments with and without ozone scrubbers attached to the tube inlet. During the sampling rate experiment, the measured diffusive uptake was constant for up to seven days for most of the VOCs tested but deviated from linearity for some of the more volatile compounds between seven and eleven days. In the ozone experiment, both exposed and unexposed tubes showed a similar decline in terpene mass over time indicating back diffusion when uncapped tubes were transferred to a clean environment but there was no indication of significant loss by ozone reaction.« less

Hydrophilic magnetic ionic liquid for magnetic headspace single-drop microextraction of chlorobenzenes prior to thermal desorption-gas chromatography-mass spectrometry.

PubMed

Fernández, Elena; Vidal, Lorena; Canals, Antonio

2017-11-23

A new, fast, easy to handle, and environmentally friendly magnetic headspace single-drop microextraction (Mag-HS-SDME) based on a magnetic ionic liquid (MIL) as an extractant solvent is presented. A small drop of the MIL 1-ethyl-3-methylimidazolium tetraisothiocyanatocobaltate(II) ([Emim] 2 [Co(NCS) 4 ]) is located on one end of a small neodymium magnet to extract nine chlorobenzenes (1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene, 1,2,3,4-tetrachlorobenzene, 1,2,4,5-tetrachlorobenzene, and pentachlorobenzene) as model analytes from water samples prior to thermal desorption-gas chromatography-mass spectrometry determination. A multivariate optimization strategy was employed to optimize experimental parameters affecting Mag-HS-SDME. The method was evaluated under optimized extraction conditions (i.e., sample volume, 20 mL; MIL volume, 1 μL; extraction time, 10 min; stirring speed, 1500 rpm; and ionic strength, 15% NaCl (w/v)), obtaining a linear response from 0.05 to 5 μg L -1 for all analytes. The repeatability of the proposed method was evaluated at 0.7 and 3 μg L -1 spiking levels and coefficients of variation ranged between 3 and 18% (n = 3). Limits of detection were in the order of nanograms per liter ranging from 4 ng L -1 for 1,4-dichlorobenzene and 1,2,3,4-tetrachlorobenzene to 8 ng L -1 for 1,2,4,5-tetrachlorobenzene. Finally, tap water, pond water, and wastewater were selected as real water samples to assess the applicability of the method. Relative recoveries varied between 82 and 114% showing negligible matrix effects. Graphical abstract Magnetic headspace single-drop microextraction followed by thermal desorption-gas chromatography-mass spectrometry.

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.

Thermal effects in nano-sized adsorbate islands growth processes at vapor deposition

NASA Astrophysics Data System (ADS)

Kharchenko, Vasyl O.; Kharchenko, Dmitrii O.; Dvornichenko, Alina V.

2016-02-01

We study a model of pattern formation in adsorptive systems with a local change in the surface temperature due to adsorption/desorption processes. It is found that thermal effects shrink the domain of main system parameters, when pattern formation is possible. It is shown that an increase in a surface reheat efficiency delays ordering processes. We have found that a distribution of adsorbate islands over sizes depends on relaxation and reheat processes. We have shown that the mean linear size of stationary adsorbate islands is of nano-meter range.

Characterisation of Dissolved Organic Carbon by Thermal Desorption - Proton Transfer Reaction - Mass Spectrometry

NASA Astrophysics Data System (ADS)

Materić, Dušan; Peacock, Mike; Kent, Matthew; Cook, Sarah; Gauci, Vincent; Röckmann, Thomas; Holzinger, Rupert

2017-04-01

Dissolved organic carbon (DOC) is an integral component of the global carbon cycle. DOC represents an important terrestrial carbon loss as it is broken down both biologically and photochemically, resulting in the release of carbon dioxide (CO2) to the atmosphere. The magnitude of this carbon loss can be affected by land management (e.g. drainage). Furthermore, DOC affects autotrophic and heterotrophic processes in aquatic ecosystems, and, when chlorinated during water treatment, can lead to the release of harmful trihalomethanes. Numerous methods have been used to characterise DOC. The most accessible of these use absorbance and fluorescence properties to make inferences about chemical composition, whilst high-performance size exclusion chromatography can be used to determine apparent molecular weight. XAD fractionation has been extensively used to separate out hydrophilic and hydrophobic components. Thermochemolysis or pyrolysis Gas Chromatography - Mass Spectrometry (GC-MS) give information on molecular properties of DOC, and 13C NMR spectroscopy can provide an insight into the degree of aromaticity. Proton Transfer Reaction - Mass Spectrometry (PTR-MS) is a sensitive, soft ionisation method suitable for qualitative and quantitative analysis of volatile and semi-volatile organic vapours. So far, PTR-MS has been used in various environmental applications such as real-time monitoring of volatile organic compounds (VOCs) emitted from natural and anthropogenic sources, chemical composition measurements of aerosols etc. However, as the method is not compatible with water, it has not been used for analysis of organic traces present in natural water samples. The aim of this work was to develop a method based on thermal desorption PTR-MS to analyse water samples in order to characterise chemical composition of dissolved organic carbon. We developed a clean low-pressure evaporation/sublimation system to remove water from samples and thermal desorption system to introduce the samples to the PTR-MS. With thermal desorption lasting just 5 min (at 200˚ C) we successfully detected more than 200 organic ions in the water samples yielding up to 800 ng/mL in total (which corresponds to 1.5% of total DOC present in the sample). Samples were from tropical peatlands in Borneo and Malaysia. Principle component analysis showed a clear separation of the samples when comparing intact and degraded peat swamp forest, and between an oil palm plantation and natural forest. This suggests that the degradation and conversion of tropical peatlands result in distinct changes to DOC composition, with possible implications for associated CO2 emissions. As the method is sensitive and reproducible it has wide potential application in the characterisation of water and of soils. It could provide important information on how land management, microbial activity, vegetation and water treatment control the chemical composition of DOC.

CO adsorption on W(100) during temperature-programmed desorption: A combined density functional theory and kinetic Monte Carlo study

NASA Astrophysics Data System (ADS)

Albao, Marvin A.; Padama, Allan Abraham B.

2017-02-01

Using a combined density functional theory (DFT) and kinetic Monte Carlo (KMC) simulations, we study the adsorption at 800 K and subsequent desorption of CO on W(100) at higher temperatures. The resulting TPD profiles are known experimentally to exhibit three desorption peaks β1, β2, and β3 at 930 K, 1070 K, and 1375 K, respectively. Unlike more recent theoretical studies that propose that all three aforementioned peaks are molecularly rather than associatively desorbed, our KMC analyses are in support of the latter, since at 800 K dissociation is facile and that CO exists as dissociation fragments C and O. We show that these peaks arise from desorption from the same adsorption site but whose binding energy varies depending on local environment, that is, the presence of CO as well as dissociation fragments C and O nearby. Furthermore we show that several key parameters, such as desorption, dissociation and recombination barriers all play a key role in the TPD spectra-these parameter effectively controls not only the location of the TPD peaks but the shape and width of the desorption peaks as well. Moreover, our KMC simulations reveal that varying the heating rate shifts the peaks but leaves their shape intact.

Exploring the nonequilibrium reactivity of molecules with platinum(111)

NASA Astrophysics Data System (ADS)

Dewitt, Kristin Marie

Various aspects of the nonequilibrium reactivity of several, catalytically important, small molecules with Pt(111)were explored. The effect of alkali metal promotion on the thermal chemistry and photochemistry of CH4,N 2, and CO2 was studied. Dissociative sticking coefficients for methane and ethane were measured as a function of gas temperature ( Tg) and surface temperature (Ts) using effusive molecular beam and angle-integrated gas dosing methods. Coupled with physisorbed complex microcanonical unimolecular rate theory these measurements provide a predictive understanding for the kinetics of these C-H bond activation reactions, i.e. allowing us to predict the sticking coefficient of CH 4 and C2H6 for any combination of T s and Tg. Work function thermal programmed desorption was used to examine the correlation between surface structure and surface work function for CH3Br and CO2. Preliminary two-photon photoemission and broad-band infrared-visible sum frequency generation experiments introduce these nonlinear spectroscopy techniques to the arsenal of surface characterization techniques available in our group. All of the disparate components of this work are tied together by one overall theme, developing an improved molecular-level understanding of the reaction dynamics of catalysis.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adib, F.; Bagreev, A.; Bandosz, T.J.

The H{sub 2}S breakthrough capacity was measured on two series of activated carbons of a coconut shell and a bituminous coal origins. To broaden the spectrum of surface features the samples were oxidized using nitric acid or ammonium persulfate under conditions chosen to preserve their pore structures. Then the carbons were characterized using Boehm titration, potentiometric titration, thermal analysis, temperature programmed desorption, sorption of nitrogen, and sorption of water. It was found that the choice of unimpregnated carbon for application as H{sub 2}S adsorbent should be made based on parameters of its acidity such as number of acidic groups, pHmore » of surface, amount of surface groups oxygen, or weight loss associated to decomposition of surface oxygen species. The results obtained from the analyses of six unimpregnated carbon samples suggest that there are certain threshold values of these quantities which, when exceeded, have a dramatic effect on the H{sub 2}S breakthrough capacity.« less

Theoretical and experimental studies of hydrogen adsorption and desorption on Ir surfaces

DOE PAGES

Kaghazchi, Payam; Jacob, Timo; Chen, Wenhua; ...

2013-06-03

Here, we report adsorption and desorption of hydrogen on planar Ir(210) and faceted Ir(210), consisting of nanoscale {311} and (110) facets, by means of temperature programmed desorption (TPD) and density functional theory (DFT) in combination with the ab initio atomistic thermodynamics approach. TPD spectra show that only one H 2 peak is seen from planar Ir(210) at all coverages whereas a single H 2 peak is observed at around 440 K (F1) at fractional monolayer (ML) coverage and an additional H 2 peak appears at around 360 K (F2) at 1 ML coverage on faceted Ir(210), implying structure sensitivity inmore » recombination and desorption of hydrogen on faceted Ir(210) versus planar Ir(210), but no evidence is found for size effects in recombination and desorption of hydrogen on faceted Ir(210) for average facet sizes of 5-14 nm. Calculations indicate that H prefers to bind at the two-fold short-bridge sites of the Ir surfaces. In addition, we studied the stability of the Ir surfaces in the presence of hydrogen at different H coverages through surface free energy plots as a function of the chemical potential, which is also converted to a temperature scale. Moreover, the calculations revealed the origin of the two TPD peaks of H 2 from faceted Ir(210): F1 from desorption of H 2 on {311} facets while F2 from desorption of H 2 on (110) facets.« less

The monolithic carbon aerogels and aerogel composites for electronics and thermal protection applications

NASA Astrophysics Data System (ADS)

Lu, Sheng; Guo, Hui; Zhou, Yugui; Liu, Yuanyuan; Jin, Zhaoguo; Liu, Bin; Zhao, Yingmin

2017-09-01

Monolithic carbon aerogels have been prepared by condensation polymerization and high temperature pyrolysis. The morphology of carbon aerogels are characterized by SEM. The pore structure is characterized by N2 adsorption-desorption technique. Monolithic carbon aerogels are mesoporous nanomaterials. Carbon fiber reinforced carbon aerogel composites are prepared by in-situ sol-gel process. Fiber reinforced carbon aerogel composites are of high mechanical strength. The thermal response of the fiber reinforced aerogel composite samples are tested in an arc plasma wind tunnel. Carbon aerogel composites show good thermal insulation capability and high temperature resistance in inert atmosphere even at ultrahigh temperature up to 1800 °C. The results show that they are suitable for applications in electrodes for supercapacitors/ Lithium-ion batteries and aerospace thermal protection area.

Displacement damage dose and implantation temperature effects on the trapping and release of deuterium implanted into SiC

NASA Astrophysics Data System (ADS)

Muñoz, P.; García-Cortés, I.; Sánchez, F. J.; Moroño, A.; Malo, M.; Hodgson, E. R.

2017-09-01

Radiation damage to flow channel insert (FCI) materials is an important issue for the concept of dual-coolant blanket development in future fusion devices. Silicon Carbide (SiC) is one of the most suitable materials for FCI. Because of the severe radiation environment and exposure to tritium during operation it is of fundamental importance to study hydrogen isotope trapping and release in these materials. Here the trapping, detrapping, and diffusion of deuterium implanted into SiC is studied in correlation with pre- and post-damage induced under different conditions. For this, SiC samples are pre-damaged with 50 keV Ne+ ions at different temperatures (20, 200, 450, 700 °C) to different damage doses (1, 3.6, 7 dpa). Next, deuterium is introduced into the samples at 450 °C by ion implantation at 7 keV. The implanted deuterium retained in the sample is analysed using secondary ion mass spectrometry (SIMS) and thermo-stimulated desorption (TSD) measurements. The results indicate that with increasing neon damage dose, the maximum deuterium desorption occurs at higher temperatures. In contrast, when increasing neon implantation temperature for a fixed dose, the maximum deuterium desorption release temperature decreases. It is interpreted that the neon bombardment produces thermally stable traps for hydrogen isotopes and the stability of this damage increases with neon pre-implantation dose. A decrease of the trapping of implanted deuterium is also observed to occur due to damage recovery by thermal annealing during pre-implantation at the higher temperatures. Finally, direct particle bombardment induced deuterium release is also observed.

Methane storage in flexible metal-organic frameworks with intrinsic thermal management

NASA Astrophysics Data System (ADS)

Mason, Jarad A.; Oktawiec, Julia; Taylor, Mercedes K.; Hudson, Matthew R.; Rodriguez, Julien; Bachman, Jonathan E.; Gonzalez, Miguel I.; Cervellino, Antonio; Guagliardi, Antonietta; Brown, Craig M.; Llewellyn, Philip L.; Masciocchi, Norberto; Long, Jeffrey R.

2015-11-01

As a cleaner, cheaper, and more globally evenly distributed fuel, natural gas has considerable environmental, economic, and political advantages over petroleum as a source of energy for the transportation sector. Despite these benefits, its low volumetric energy density at ambient temperature and pressure presents substantial challenges, particularly for light-duty vehicles with little space available for on-board fuel storage. Adsorbed natural gas systems have the potential to store high densities of methane (CH4, the principal component of natural gas) within a porous material at ambient temperature and moderate pressures. Although activated carbons, zeolites, and metal-organic frameworks have been investigated extensively for CH4 storage, there are practical challenges involved in designing systems with high capacities and in managing the thermal fluctuations associated with adsorbing and desorbing gas from the adsorbent. Here, we use a reversible phase transition in a metal-organic framework to maximize the deliverable capacity of CH4 while also providing internal heat management during adsorption and desorption. In particular, the flexible compounds Fe(bdp) and Co(bdp) (bdp2- = 1,4-benzenedipyrazolate) are shown to undergo a structural phase transition in response to specific CH4 pressures, resulting in adsorption and desorption isotherms that feature a sharp ‘step’. Such behaviour enables greater storage capacities than have been achieved for classical adsorbents, while also reducing the amount of heat released during adsorption and the impact of cooling during desorption. The pressure and energy associated with the phase transition can be tuned either chemically or by application of mechanical pressure.

Coverage-dependent adsorption and desorption of oxygen on Pd(100)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dunnen, Angela den; Jacobse, Leon; Wiegman, Sandra

2016-06-28

We have studied the adsorption and desorption of O{sub 2} on Pd(100) by supersonic molecular beam techniques and thermal desorption spectroscopy. Adsorption measurements on the bare surface confirm that O{sub 2} initially dissociates for all kinetic energies between 56 and 380 meV and surface temperatures between 100 and 600 K via a direct mechanism. At and below 150 K, continued adsorption leads to a combined O/O{sub 2} overlayer. Dissociation of molecularly bound O{sub 2} during a subsequent temperature ramp leads to unexpected high atomic oxygen coverages, which are also obtained at high incident energy and high surface temperature. At intermediatemore » temperatures and energies, these high final coverages are not obtained. Our results show that kinetic energy of the gas phase reactant and reaction energy dissipated during O{sub 2} dissociation on the cold surface both enable activated nucleation of high-coverage surface structures. We suggest that excitation of local substrate phonons may play a crucial role in oxygen dissociation at any coverage.« less

Technical specification for vacuum systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khaw, J.

The vacuum systems at the Stanford Linear Accelerator Center (SLAC) are primarily of all-metal construction and operate at pressures from 10/sup -5/ to 10/sup -11/ Torr. The primary gas loads during operation result from thermal desorption and beam-induced desorption from the vacuum chamber walls. These desorption rates can be extremely high in the case of hydrocarbons and other contaminants. These specifications place a major emphasis on eliminating contamination sources. The specifications and procedures have been written to insure the cleanliness and vacuum integrity of all SLAC vacuum systems, and to assist personnel involved with SLAC vacuum systems in choosing andmore » designing components that are compatible with existing systems and meet the quality and reliability of SLAC vacuum standards. The specification includes requirements on design, procurement, fabrication, chemical cleaning, clean room practices, welding and brazing, helium leak testing, residual gas analyzer testing, bakeout, venting, and pumpdown. Also appended are specifications regarding acceptable vendors, isopropyl alcohol, bakeable valve cleaning procedure, mechanical engineering safety inspection, notes on synchrotron radiation, and specifications of numerous individual components. (LEW)« less

Rate equation analysis of hydrogen uptake on Si (100) surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Inanaga, S.; Rahman, F.; Khanom, F.

2005-09-15

We have studied the uptake process of H on Si (100) surfaces by means of rate equation analysis. Flowers' quasiequilibrium model for adsorption and desorption of H [M. C. Flowers, N. B. H. Jonathan, A. Morris, and S. Wright, Surf. Sci. 396, 227 (1998)] is extended so that in addition to the H abstraction (ABS) and {beta}{sub 2}-channel thermal desorption (TD) the proposed rate equation further includes the adsorption-induced desorption (AID) and {beta}{sub 1}-TD. The validity of the model is tested by the experiments of ABS and AID rates in the reaction system H+D/Si (100). Consequently, we find it canmore » well reproduce the experimental results, validating the proposed model. We find the AID rate curve as a function of surface temperature T{sub s} exhibits a clear anti-correlation with the bulk dangling bond density versus T{sub s} curve reported in the plasma-enhanced chemical vapor deposition (CVD) for amorphous Si films. The significance of the H chemistry in plasma-enhanced CVD is discussed.« less

A combined model of heat and mass transfer for the in situ extraction of volatile water from lunar regolith

NASA Astrophysics Data System (ADS)

Reiss, P.

2018-05-01

Chemical analysis of lunar soil samples often involves thermal processing to extract their volatile constituents, such as loosely adsorbed water. For the characterization of volatiles and their bonding mechanisms it is important to determine their desorption temperature. However, due to the low thermal diffusivity of lunar regolith, it might be difficult to reach a uniform heat distribution in a sample that is larger than only a few particles. Furthermore, the mass transport through such a sample is restricted, which might lead to a significant delay between actual desorption and measurable outgassing of volatiles from the sample. The entire volatiles extraction process depends on the dynamically changing heat and mass transfer within the sample, and is influenced by physical parameters such as porosity, tortuosity, gas density, temperature and pressure. To correctly interpret measurements of the extracted volatiles, it is important to understand the interaction between heat transfer, sorption, and gas transfer through the sample. The present paper discusses the molecular kinetics and mechanisms that are involved in the thermal extraction process and presents a combined parametrical computation model to simulate this process. The influence of water content on the gas diffusivity and thermal diffusivity is discussed and the issue of possible resorption of desorbed molecules within the sample is addressed. Based on the multi-physical computation model, a case study for the ProSPA instrument for in situ analysis of lunar volatiles is presented, which predicts relevant dynamic process parameters, such as gas pressure and process duration.

Surface area and pore size characteristics of nanoporous gold subjected to thermal, mechanical, or surface modification studied using gas adsorption isotherms, cyclic voltammetry, thermogravimetric analysis, and scanning electron microscopy

PubMed Central

Tan, Yih Horng; Davis, Jason A.; Fujikawa, Kohki; Ganesh, N. Vijaya; Demchenko, Alexei V.

2012-01-01

Nitrogen adsorption/desorption isotherms are used to investigate the Brunauer, Emmett, and Teller (BET) surface area and Barrett-Joyner-Halenda (BJH) pore size distribution of physically modified, thermally annealed, and octadecanethiol functionalized np-Au monoliths. We present the full adsorption-desorption isotherms for N2 gas on np-Au, and observe type IV isotherms and type H1 hysteresis loops. The evolution of the np-Au under various thermal annealing treatments was examined using scanning electron microscopy (SEM). The images of both the exterior and interior of the thermally annealed np-Au show that the porosity of all free standing np-Au structures decreases as the heat treatment temperature increases. The modification of the np-Au surface with a self-assembled monolayer (SAM) of C18-SH (coverage of 2.94 × 1014 molecules cm−2 based from the decomposition of the C18-SH using thermogravimetric analysis (TGA)), was found to reduce the strength of the interaction of nitrogen gas with the np-Au surface, as reflected by a decrease in the ‘C’ parameter of the BET equation. From cyclic voltammetry studies, we found that the surface area of the np-Au monoliths annealed at elevated temperatures followed the same trend with annealing temperature as found in the BET surface area study and SEM morphology characterization. The study highlights the ability to control free-standing nanoporous gold monoliths with high surface area, and well-defined, tunable pore morphology. PMID:22822294

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.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scherwitzl, Boris; Lassnig, Roman; Truger, Magdalena

The evaporation of quinacridone from a stainless steel Knudsen cell leads to the partial decomposition of this molecule in the cell, due to its comparably high sublimation temperature. At least one additional type of molecules, namely indigo, could be detected in the effusion flux. Thermal desorption spectroscopy and atomic force microscopy have been used to study the co-deposition of these molecules on sputter-cleaned and carbon-covered silicon dioxide surfaces. Desorption of indigo appears at temperatures of about 400 K, while quinacridone desorbs at around 510 K. For quinacridone, a desorption energy of 2.1 eV and a frequency factor for desorption ofmore » 1 × 10{sup 19} s{sup −1} were calculated, which in this magnitude is typical for large organic molecules. A fraction of the adsorbed quinacridone molecules (∼5%) decomposes during heating, nearly independent of the adsorbed amount, resulting in a surface composed of small carbon islands. The sticking coefficients of indigo and quinacridone were found to be close to unity on a carbon covered SiO{sub 2} surface but significantly smaller on a sputter-cleaned substrate. The reason for the latter can be attributed to insufficient energy dissipation for unfavorably oriented impinging molecules. However, due to adsorption via a hot-precursor state, the sticking probability is increased on the surface covered with carbon islands, which act as accommodation centers.« less

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.

Note: A versatile mass spectrometer chamber for molecular beam and temperature programmed desorption experiments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tonks, James P., E-mail: james.tonks@awe.co.uk; AWE Plc, Aldermaston, Reading, Berkshire RG7 4PR; Galloway, Ewan C., E-mail: ewan.galloway@awe.co.uk

2016-08-15

A dual purpose mass spectrometer chamber capable of performing molecular beam scattering (MBS) and temperature programmed desorption (TPD) is detailed. Two simple features of this design allow it to perform these techniques. First, the diameter of entrance aperture to the mass spectrometer can be varied to maximize signal for TPD or to maximize angular resolution for MBS. Second, the mass spectrometer chamber can be radially translated so that it can be positioned close to the sample to maximize signal or far from the sample to maximize angular resolution. The performance of this system is described and compares well with systemsmore » designed for only one of these techniques.« less

Novel Process for Removal and Recovery of Vapor Phase Mercury

DOE Office of Scientific and Technical Information (OSTI.GOV)

Greenwell, Collin; Roberts, Daryl L; Albiston, Jason

We demonstrated in the Phase I program all key attributes of a new technology for removing mercury from flue gases, namely, a) removal of greater than 95% of both elemental and oxidized forms of mercury, both in the laboratory and in the field b) regenerability of the sorbent c) ability to scale up, and d) favorable economics. The Phase I program consisted of four tasks other than project reporting: Task I-1 Screen Sorbent Configurations in the Laboratory Task I-2 Design and Fabricate Bench-Scale Equipment Task I-3 Test Bench-Scale Equipment on Pilot Combustor Task I-4 Evaluate Economics Based on Bench-Scale Resultsmore » In Task I-1, we demonstrated that the sorbents are thermally durable and are regenerable through at least 55 cycles of mercury uptake and desorption. We also demonstrated two low-pressure- drop configurations of the sorbent, namely, a particulate form and a monolithic form. We showed that the particulate form of the sorbent would take up 100% of the mercury so long as the residence time in a bed of the sorbent exceeded 0.1 seconds. In principle, the particulate form of the sorbent could be imbedded in the back side of a higher temperature bag filter in a full-scale application. With typical bag face velocities of four feet per minute, the thickness of the particulate layer would need to be about 2000 microns to accomplish the uptake of the mercury. For heat transfer efficiency, however, we believed the monolithic form of the sorbent would be the more practical in a full scale application. Therefore, we purchased commercially-available metallic monoliths and applied the sorbent to the inside of the flow channels of the monoliths. At face velocities we tested (up to 1.5 ft/sec), these monoliths had less than 0.05 inches of water pressure drop. We tested the monolithic form of the sorbent through 21 cycles of mercury sorption and desorption in the laboratory and included a test of simultaneous uptake of both mercury and mercuric chloride. Overall, in Task I-1, we found that the particulate and monolith forms of the sorbent were thermally stable and durable and would repeatedly sorb and desorb 100% of the mercury, including mercuric chloride, with low pressure drop and short residence times at realistic flue gas conditions.« less

Day-night differences in the composition and sources of carbonaceous aerosol at a polluted regional background site in the Netherlands

NASA Astrophysics Data System (ADS)

Dusek, Ulrike; Broekema, Elise; Holzinger, Rupert; Röckmann, Thomas; Meijer, Harro

2017-04-01

The origin of carbonaceous aerosol differs during day- and night-time, because emissions from major sources such as traffic, biomass combustion, and secondary organic aerosol formation show a distinct diurnal pattern. Moreover, photochemical processing and evaporation of semi-volatile organic compounds are enhanced during day-time, due to the availability of sunlight and higher temperatures. Assessing day-night differences in sources and chemical composition can give an indication of the importance of local/regional carbon sources and processing, since day-night differences should be averaged out during long-range transport. If local sources dominate, one could expect a strong diurnal variation in the source profile, but if long-range transport dominates the diurnal variation would be much weaker. In this study we measure the isotopic (14C and 13C) and detailed chemical composition of the organic fraction of the aerosol on high volume PM2.5 filter samples that were collected separately during day and night time. Radiocarbon (14C) measurements are used to estimate three main aerosol sources of organic and elemental carbon (OC and EC): Fossil fuel combustion (ff), biomass combustion (bb), and biogenic sources (bio). The detailed chemical and stable isotopic composition are measured at different desorption temperatures from the filter, which separates the more and less refractory organic compounds. The composition of the organic aerosol is measured using an thermal-desporption Proton Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-ToF-MS) method (Holzinger et al, 2010) and the stable isotopic composition is measured using a thermal desorption IRMS method (Dusek et al., 2013). Source apportionment results using 14C show that the contribution of fossil fuel combustion to EC and OC is higher during day-time than during night-time. This is valid for all seasons. During night-time biomass combustion plays a bigger role as a source of carbonaceous aerosol. Even in the summer, when biomass combustion is a small source, its relative contribution increases between 19:00 and 07:00. However, the diurnal changes in source contributions are relatively moderate (e.g., the biomass burning contribution to TC increased from 31% to 43% for the winter sample with the most distinct day-night difference.) This highlights the importance of long-range transport as a source of the carbonaceous aerosol in this region. First results from chemical composition measurements on four of the samples show that the concentration of less refractory organic carbon (desorption temperature up to 200 °C) increases at night-time much more strongly than the concentration of the more refractory carbon. Similarly, the concentration of small organic compounds with m/z < 100 also increases more strongly than heavier compounds. This indicates partitioning of semi-volatile OC as a possible additional night-time source. The chemical composition will be studied in more detail, focusing on diurnal changes in O/C ratios, individual compounds and compound classes, such as hydrocarbons or organic acids. Dusek, U., Meusinger, C., Oyama, B., Ramon, W., de Wilde, P., Holzinger, R., and Röckmann, T.: A thermal desorption system for measuring δ 13 C ratios on organic aerosol, Journal of aerosol science, 66, 72-82, 2013. Holzinger, R., Williams, J., Herrmann, F., Lelieveld, J., Donahue, N., Röckmann, T., 2010. Aerosol analysis using a Thermal-Desorption Proton-Transfer-Reaction Mass Spectrometer (TD-PTR-MS): a new approach to study processing of organic aerosols. Atmospheric chemistry and physics 10, 2257-2267.

Photodesorption of Solid CO2 by Lyα

NASA Astrophysics Data System (ADS)

Bahr, D. A.; Baragiola, R. A.

2012-12-01

We measured desorption of atoms and molecules from films of solid carbon dioxide in an ultrahigh vacuum from 6 to 60 K under irradiation with Lyα (121.6 nm, 10.2 eV) photons, an important process in the balance between gas phase and condensed molecules in the interstellar medium. The measurements use microgravimetry and mass spectrometry during irradiation and temperature programmed desorption after irradiation. At low photon fluences, the desorption flux consists mainly of O atoms and, after ~1017 photons cm-2, it is dominated by CO with smaller amount of O2, C, and CO2, with the presence of O2 indicating solid-state chemical reactions. At high fluences (up to 1018 photons cm-2), the desorption yields saturate at values much higher than in previous studies. The yields (molecules/photon), derived assuming stoichiometric desorption, reach 0.014 at 6 K, growing to ~0.2 at 50 and 60 K. Warming the films during irradiation gives rise to pressure spikes that suggest desorption of trapped species in pores or at defects, possibly assisted by radical-induced reactions. Such an effect could be significant for radiation-processed CO2-coated interstellar grains that are heated by, i.e., cosmic ray impacts or grain-grain collisions. We discuss the experiments considering photochemical mechanisms and compare them to the results of ion irradiation.

Investigation of molecule-adsorption kinetics by a pulsed laser desorption technique

NASA Astrophysics Data System (ADS)

Varakin, V. N.; Lozovskii, A. D.; Panesh, A. M.; Simonov, A. P.

1987-02-01

The laser thermal desorption technique is used to measure the adsorption kinetics of SO2 and CO molecules on stainless steel with the aim of investigating the initial stage of oxidation of the steel by adsorbed CO molecules. Attention is given to the dependence of the rate of establishment of the equilibrium concentration of adsorbed molecules on SO2-gas pressure; CO adsorption kinetics on stainless steel at a gas pressure of 9 x 10 to the -8th torr; and the dependence of the concentration of adsorbed CO molecules on exposure in the gas at a pressure of 9 x 10 to the -8th torr under irradiation by laser pulses with repetition periods of 1-2, 2-4, 3-6, and 4-8 min.

CO2 hydrogenation on a metal hydride surface.

PubMed

Kato, Shunsuke; Borgschulte, Andreas; Ferri, Davide; Bielmann, Michael; Crivello, Jean-Claude; Wiedenmann, Daniel; Parlinska-Wojtan, Magdalena; Rossbach, Peggy; Lu, Ye; Remhof, Arndt; Züttel, Andreas

2012-04-28

The catalytic hydrogenation of CO(2) at the surface of a metal hydride and the corresponding surface segregation were investigated. The surface processes on Mg(2)NiH(4) were analyzed by in situ X-ray photoelectron spectroscopy (XPS) combined with thermal desorption spectroscopy (TDS) and mass spectrometry (MS), and time-of-flight secondary ion mass spectrometry (ToF-SIMS). CO(2) hydrogenation on the hydride surface during hydrogen desorption was analyzed by catalytic activity measurement with a flow reactor, a gas chromatograph (GC) and MS. We conclude that for the CO(2) methanation reaction, the dissociation of H(2) molecules at the surface is not the rate controlling step but the dissociative adsorption of CO(2) molecules on the hydride surface. This journal is © the Owner Societies 2012

Effects of Potassium loading and thermal aging on K/Pt/Al2O3 high-temperature lean NOx trap catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luo, Jinyong; Gao, Feng; Kim, Do Heui

2014-03-31

The effects of K loading and thermal aging on the structural properties and high temperature performance of Pt/K/Al2O3 lean NOx trap (LNT) catalysts were investigated using in situ X-ray diffraction (XRD), temperature-programmed decomposition/desorption of NOx (NOx-TPD), transmission electron microscopy (TEM), NO oxidation and NOx storage tests. In situ XRD results demonstrate that KNO3 becomes extremely mobile on the Al2O3 surface, and experiences complex transformations between orthorhombic and rhombohedral structures, accompanied by sintering, melting and thermal decomposition upon heating. NOx storage results show an optimum K loading around 10% for the best performance at high temperatures. At lower K loadings wheremore » the majority of KNO3 stays as a surface layer, the strong interaction between KNO3 and Al2O3 promotes KNO3 decomposition and deteriorates high-temperature performance. At K loadings higher than 10%, the performance drop is not caused by NOx diffusion limitations as for the case of barium-based LNTs, but rather from the blocking of Pt sites by K species, which adversely affects NO oxidation. Thermal aging at 800 ºC severely deactivates the Pt/K/Al2O3 catalysts due to Pt sintering. However, in the presence of potassium, some Pt remains in a dispersed and oxidized form. These Pt species interact strongly with K and, therefore, do not sinter. After a reduction treatment, these Pt species remain finely dispersed, contributing to a partial recovery of NOx storage performance.« less

CO Diffusion and Desorption Kinetics in CO2 Ices

NASA Astrophysics Data System (ADS)

Cooke, Ilsa R.; Öberg, Karin I.; Fayolle, Edith C.; Peeler, Zoe; Bergner, Jennifer B.

2018-01-01

The diffusion of species in icy dust grain mantles is a fundamental process that shapes the chemistry of interstellar regions; yet, measurements of diffusion in interstellar ice analogs are scarce. Here we present measurements of CO diffusion into CO2 ice at low temperatures (T = 11–23 K) using CO2 longitudinal optical phonon modes to monitor the level of mixing of initially layered ices. We model the diffusion kinetics using Fick’s second law and find that the temperature-dependent diffusion coefficients are well fit by an Arrhenius equation, giving a diffusion barrier of 300 ± 40 K. The low barrier along with the diffusion kinetics through isotopically labeled layers suggest that CO diffuses through CO2 along pore surfaces rather than through bulk diffusion. In complementary experiments, we measure the desorption energy of CO from CO2 ices deposited at 11–50 K by temperature programmed desorption and find that the desorption barrier ranges from 1240 ± 90 K to 1410 ± 70 K depending on the CO2 deposition temperature and resultant ice porosity. The measured CO–CO2 desorption barriers demonstrate that CO binds equally well to CO2 and H2O ices when both are compact. The CO–CO2 diffusion–desorption barrier ratio ranges from 0.21 to 0.24 dependent on the binding environment during diffusion. The diffusion–desorption ratio is consistent with the above hypothesis that the observed diffusion is a surface process and adds to previous experimental evidence on diffusion in water ice that suggests surface diffusion is important to the mobility of molecules within interstellar ices.

Microhardness, Friction and Wear of SiC and Si3N4 Materials as a Function of Load, Temperature and Environment.

DTIC Science & Technology

1980-10-01

rather than by microplasticity . At 500 C, on the other hand, Si showed substantial crack tip plasticity. Koss and Chan (47) have studied fracture along...materials prone to such chemomechanical effects, thermal desorption of adsorbed species will result in changes in hardness behaviour in addition to the

COMPARISON OF 24H AVERAGE VOC MONITORING RESULTS FOR RESIDENTIAL INDOOR AND OUTDOOR AIR USING CARBOPACK X-FILLED DIFFUSIVE SAMPLERS AND ACTIVE SAMPLING - A PILOT STUDY

EPA Science Inventory

Analytical results obtained by thermal desorption GC/MS for 24h diffusive sampling of 11 volatile organic compounds (VOCs) are compared with results of time-averaged active sampling at a known constant flow rate. Air samples were collected with co-located duplicate diffusive samp...

Stir bar sorptive extraction with EG-Silicone coating for bisphenols determination in personal care products by GC-MS.

PubMed

Cacho, Juan Ignacio; Campillo, Natalia; Viñas, Pilar; Hernández-Córdoba, Manuel

2013-05-05

An easy to perform analytical method for the determination of three bisphenol compounds (BPs) in commonly used personal care products (PCPs) is presented. Ethylene glycol-silicone (EG-Silicone) coated stir bars, which have recently become commercially available, are evaluated in this study for the simultaneous determination of bisphenol A (BPA), bisphenol F (BPF) and bisphenol Z (BPZ) by stir bar sorptive extraction (SBSE) in combination with thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS). This new sorptive extraction phase allows the analysis of these compounds without any previous derivatization procedure. Different parameters affecting both SBSE extraction and thermal desorption were carefully optimized, using experimental designs based on the Taguchi orthogonal arrays. The procedure was applied to analyzing easily bought PCPs, providing detection limits of about 8 ng g(-1), with precisions lower than 11% in terms of relative standard deviation. Recovery studies performed at two different concentration levels provided satisfactory values for all the compounds. The analyzed personal care samples contained BPA at concentration levels ranging from 30.9 to 88.3 ng g(-1). Copyright © 2013 Elsevier B.V. All rights reserved.

Distinguishing chinese star anise from Japanese star anise using thermal desorption-gas chromatography-mass spectrometry.

PubMed

Howes, Melanie-Jayne R; Kite, Geoffrey C; Simmonds, Monique S J

2009-07-08

The volatile compounds from the pericarps of Illicium anisatum L., Illicium brevistylum A.C.Sm., Illicium griffithii Hook.f. & Thomson, Illicium henryi Diels, Illicium lanceolatum A.C.Sm., Illicium majus Hook.f. & Thomson, Illicium micranthum Dunn, and Illicium verum Hook.f. were examined by thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS). The volatiles desorbed from the pericarps of I. verum (Chinese star anise), the species traded for culinary purposes, were generally characterized by a high proportion of (E)-anethole (57.6-77.1%) and the presence of foeniculin; the latter was otherwise only detected in the pericarps of I. lanceolatum. In the pericarps of all other species analyzed, the percentage composition of (E)-anethole was comparatively lower (

Stir bar sorptive extraction-thermal desorption-gas chromatography-mass spectrometry: an effective tool for determining persistent organic pollutants and nonylphenol in coastal waters in compliance with existing Directives.

PubMed

Sánchez-Avila, Juan; Quintana, Jordi; Ventura, Francesc; Tauler, Romà; Duarte, Carlos M; Lacorte, Silvia

2010-01-01

A multi-residual method based on stir bar sorptive extraction coupled with thermal desorption-gas chromatography-mass spectrometry (SBSE-TD-GC-MS) has been developed to measure 49 organic pollutants (organochlorine pesticides, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, polybrominated diphenyl ethers and nonylphenol) in seawater. Using 100ml of water, the method exhibited good linearity, with recoveries between 86% and 118% and relative standard deviation between 2% and 24% for almost all compounds. The method was applied to determine target contaminants in Catalonian seawater, including coastal areas, ports and desalination plant feed water. Overall individual compound levels oscillated between 0.16 and 597 ng l(-1); PAHs and nonylpenol were the compounds found at the highest concentrations. The method provided LODs between 0.011 and 2.5 ng l(-1), lower than the Environmental Quality Standards (EQS) fixed by Directive 2008/105/EC. In compliance with the directive, this method can be used as a tool to survey target compounds and is aimed at protecting coastal ecosystems from chemical pollution. Copyright 2009 Elsevier Ltd. All rights reserved.

China action of "Cleanup Plan for Polychlorinated Biphenyls Burial Sites": emissions during excavation and thermal desorption of a capacitor-burial site.

PubMed

Yang, Bing; Zhou, Lingli; Xue, Nandong; Li, Fasheng; Wu, Guanglong; Ding, Qiong; Yan, Yunzhong; Liu, Bo

2013-10-01

Scarce data are available so far on emissions in a given scenario for excavation and thermal desorption, a common practice, of soils contaminated with polychlorinated biphenyls (PCBs). As part of China action of "Cleanup Plan for PCBs Burial Sites", this study roughly estimated PCBs emissions in the scenario for a capacitor-burial site. The concentrations of total PCBs (22 congeners) in soils were in the range of 2.1-16,000μg/g with a mean of 2300μg/g, among the same order of magnitude as the highest values obtained in various PCBs-contaminated sites. Only six congeners belonging to Di-, Tri-, and Tetra-CBs were observed above limits of detection in air samples in the scenario, partially which can be estimated by the USEPA air emission model. Comparing concentrations and composition profiles of PCBs in the soil and air samples further indicated a leaked source of commercial PCBs formulations of trichlorobiphenyl (China PCB no. 1). The measures taken if any to mitigate the volatilization and movement of PCBs and to minimize worker exposure were discussed for improvements of the excavation practice. Copyright © 2013 Elsevier Inc. All rights reserved.

Remediation of 1,2,3-trichlorobenzene contaminated soil using a combined thermal desorption-molten salt oxidation reactor system.

PubMed

Li, Jin-hui; Sun, Xiao-fei; Yao, Zhi-tong; Zhao, Xiang-yang

2014-02-01

A combined thermal desorption (TD)-molten salt oxidation (MSO) reactor system was applied to remediate the 1,2,3-trichlorobenzene (1,2,3-TCB) contaminated soil. The TD reactor was used to enrich the contaminant from soil, and its dechlorination of the contaminant was achieved in the MSO reactor. The optimum operating conditions of TD, and the effects of MSO reactor temperatures, additive amounts of the TCB on destruction and removal efficiency (DRE) of TCB and chlorine retention efficiency (CRE) were investigated. The reaction mechanism and pathway were proposed as well. The combined system could remediate the contaminated soil at a large scale of concentration from 5 to 25gkg(-1), and the DRE and CRE reached more than 99% and 95%, respectively, at temperatures above 850°C. The reaction emissions included C6H6, CH4, CO and CO2, and chlorinated species were not detected. It was found that a little increase in the temperature can considerably reduce the emission of C6H6, CH4, and CO, while the CO2 level increased. Copyright © 2014. Published by Elsevier Ltd.

Kinetic compensation effect in the thermal desorption of a binary gas mixture

NASA Astrophysics Data System (ADS)

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

The kinetic compensation effect, observed in many different areas of science, is the systematic change in the magnitudes of the Arrhenius parameters Ea, the energy of activation and ν, the preexponential factor, as a response to external perturbing parameters. Its existence continues to be debated as it has not been explicitly demonstrated and its physical origins remain poorly understood. As part of a systematic study of different factors that alter the energy of activation during thermal desorption, we have performed numerical studies of the effects of adsorbate-adsorbate interactions on the Arrhenius parameters, as well as the effects of changes in surface morphology. Our results have consistently shown that there is a partial compensation effect between Ea and lnν and a tendency towards isokinetic equilibrium when the system transitions from an interacting to a non-interacting regime. In the present work we study the effects of the presence of two different chemical species. With our systematic study we expect to provide a deeper insight into the microscopic events that originate compensation effects, not only in our system, but also in other fields where these effects have been reported.

Stir bar sorptive extraction coupled to gas chromatography-mass spectrometry for the determination of bisphenols in canned beverages and filling liquids of canned vegetables.

PubMed

Cacho, J I; Campillo, N; Viñas, P; Hernández-Córdoba, M

2012-07-20

This paper describes a method for the simultaneous determination of bisphenol A (BPA), bisphenol F (BPF), bisphenol Z (BPZ) and biphenol (BP), using stir bar sorptive extraction (SBSE) in combination with thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS). Several parameters affecting both extraction and thermal desorption of the SBSE stages were carefully optimized by multivariate designs. SBSE was performed with two derivatization procedures, in situ acetylation and in tube silylation, and the results were compared with those obtained when the analytes were not derivatized. The proposed method, determining the analytes as acyl derivatives, was applied to analyze commercially canned beverages, as well as the filling liquids of canned vegetables, providing detection limits of between 4.7 and 12.5 ng L⁻¹, depending on the compound. The intraday and interday precisions were lower than 6% in terms of relative standard deviation. Recovery studies at two concentration levels, 0.1 and 1 μg L⁻¹, were performed providing recoveries in the 86-122% range. The samples analyzed contained higher concentrations of BPA than of the other analytes. Copyright © 2012 Elsevier B.V. All rights reserved.

Rapid Quantification of N-Methyl-2-pyrrolidone in Polymer Matrices by Thermal Desorption-GC/MS.

PubMed

Kim, Young-Min; Kim, Jae Woo; Moon, Hye Mi; Lee, Min-Jin; Hosaka, Akihiko; Watanabe, Atsushi; Teramae, Norio; Park, Young-Kwon; Myung, Seung-Woon

2017-01-01

Analysis of a residual solvent in polymeric materials has become an important issue due to the increased regulations and standards for its use. N-Methyl-2-pyrrolidone (NMP) is a solvent widely used in many industries and restricted as one of the chemicals under EU REACH regulations due to its potential harmful effects. In this study, thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) is applied for the quantitative analysis of NMP with the use of a polymer-coated sample cup. By using the polymer-coated sample cup, the vaporization of NMP was prevented during waiting time before TD-GC/MS analysis. The calibration curve for the TD method showed good linearity (correlation coefficient, r 2 = 0.9998) and precision values (below 5.3% RSD). NMP recovery rates in different polymer matrices (PS, PMMA and PVC) were in the range of 98.8 to 106.6% with RSD values below 5.0%. The quantification result (600 mg NMP/kg PVC) for the blind NMP carrying sample in a PVC matrix by TD-GC/MS was higher than that (532 mg NMP/kg PVC) by solvent extraction-GC/MS method.

Fast and solvent-free quantitation of boar taint odorants in pig fat by stable isotope dilution analysis-dynamic headspace-thermal desorption-gas chromatography/time-of-flight mass spectrometry.

PubMed

Fischer, Jochen; Haas, Torsten; Leppert, Jan; Lammers, Peter Schulze; Horner, Gerhard; Wüst, Matthias; Boeker, Peter

2014-09-01

Boar taint is a specific off-odour of boar meat products, known to be caused by at least three unpleasant odorants, with very low odour thresholds. Androstenone is a boar pheromone produced in the testes, whereas skatole and indole originate from the microbial breakdown of tryptophan in the intestinal tract. A new procedure, applying stable isotope dilution analysis (SIDA) and dynamic headspace-thermal desorption-gas chromatography/time-of-flight mass spectrometry (dynHS-TD-GC/TOFMS) for the simultaneous quantitation of these boar taint compounds in pig fat was elaborated and validated in this paper. The new method is characterised by a simple and solvent-free dynamic headspace sampling. The deuterated compounds d3-androstenone, d3-skatole and d6-indole were used as internal standards to eliminate matrix effects. The method validation performed revealed low limits of detection (LOD) and quantitation (LOQ) with high accuracy and precision, thus confirming the feasibility of the new dynHS-TD-GC/TOFMS approach for routine analysis. Copyright © 2014 Elsevier Ltd. All rights reserved.

Laser Pulse Width Dependence and Ionization Mechanism of Matrix-Assisted Laser Desorption/Ionization

NASA Astrophysics Data System (ADS)

Liang, Sheng-Ping; Lu, I.-Chung; Tsai, Shang-Ting; Chen, Jien-Lian; Lee, Yuan Tseh; Ni, Chi-Kung

2017-10-01

Ultraviolet laser pulses at 355 nm with variable pulse widths in the region from 170 ps to 1.5 ns were used to investigate the ionization mechanism of matrix-assisted laser desorption/ionization (MALDI) for matrices 2,5-dihydroxybenzoic acid (DHB), α-cyano-4-hydroxycinnamic acid (CHCA), and sinapinic acid (SA). The mass spectra of desorbed ions and the intensity and velocity distribution of desorbed neutrals were measured simultaneously for each laser shot. These quantities were found to be independent of the laser pulse width. A comparison of the experimental measurements and numerical simulations according to the multiphoton ionization, coupled photophysical and chemical dynamics (CPCD), and thermally induced proton transfer models showed that the predictions of thermally induced proton transfer model were in agreement with the experimental data, but those of the multiphoton ionization model were not. Moreover, the predictions of the CPCD model based on singlet-singlet energy pooling were inconsistent with the experimental data of CHCA and SA, but were consistent with the experimental data of DHB only when some parameters used in the model were adjusted to extreme values. [Figure not available: see fulltext.

Thermal Desorption Analysis of Effective Specific Soil Surface Area

NASA Astrophysics Data System (ADS)

Smagin, A. V.; Bashina, A. S.; Klyueva, V. V.; Kubareva, A. V.

2017-12-01

A new method of assessing the effective specific surface area based on the successive thermal desorption of water vapor at different temperature stages of sample drying is analyzed in comparison with the conventional static adsorption method using a representative set of soil samples of different genesis and degree of dispersion. The theory of the method uses the fundamental relationship between the thermodynamic water potential (Ψ) and the absolute temperature of drying ( T): Ψ = Q - aT, where Q is the specific heat of vaporization, and a is the physically based parameter related to the initial temperature and relative humidity of the air in the external thermodynamic reservoir (laboratory). From gravimetric data on the mass fraction of water ( W) and the Ψ value, Polyanyi potential curves ( W(Ψ)) for the studied samples are plotted. Water sorption isotherms are then calculated, from which the capacity of monolayer and the target effective specific surface area are determined using the BET theory. Comparative analysis shows that the new method well agrees with the conventional estimation of the degree of dispersion by the BET and Kutilek methods in a wide range of specific surface area values between 10 and 250 m2/g.

Development of the GC-MS organic aerosol monitor (GC-MS OAM) for in-field detection of particulate organic compounds

NASA Astrophysics Data System (ADS)

Cropper, Paul M.; Overson, Devon K.; Cary, Robert A.; Eatough, Delbert J.; Chow, Judith C.; Hansen, Jaron C.

2017-11-01

Particulate matter (PM) is among the most harmful air pollutants to human health, but due to its complex chemical composition is poorly characterized. A large fraction of PM is composed of organic compounds, but these compounds are not regularly monitored due to limitations in current sampling and analysis techniques. The Organic Aerosol Monitor (GC-MS OAM) combines a collection device with thermal desorption, gas chromatography and mass spectrometry to quantitatively measure the carbonaceous components of PM on an hourly averaged basis. The GC-MS OAM is fully automated and has been successfully deployed in the field. It uses a chemically deactivated filter for collection followed by thermal desorption and GC-MS analysis. Laboratory tests show that detection limits range from 0.2 to 3 ng for 16 atmospherically relevant compounds, with the possibility for hundreds more. The GC-MS OAM was deployed in the field for semi-continuous measurement of the organic markers, levoglucosan, dehydroabietic acid, and polycyclic aromatic hydrocarbons (PAHs) from January to March 2015. Results illustrate the significance of this monitoring technique to characterize the organic components of PM and identify sources of pollution.

Surface chemistry in photodissociation regions

NASA Astrophysics Data System (ADS)

Esplugues, G. B.; Cazaux, S.; Meijerink, R.; Spaans, M.; Caselli, P.

2016-06-01

Context. The presence of dust can strongly affect the chemical composition of the interstellar medium. We model the chemistry in photodissociation regions (PDRs) using both gas-phase and dust-phase chemical reactions. Aims: Our aim is to determine the chemical compositions of the interstellar medium (gas/dust/ice) in regions with distinct (molecular) gas densities that are exposed to radiation fields with different intensities. Methods: We have significantly improved the Meijerink PDR code by including 3050 new gas-phase chemical reactions and also by implementing surface chemistry. In particular, we have included 117 chemical reactions occurring on grain surfaces covering different processes, such as adsorption, thermal desorption, chemical desorption, two-body reactions, photo processes, and cosmic-ray processes on dust grains. Results: We obtain abundances for different gas and solid species as a function of visual extinction, depending on the density and radiation field. We also analyse the rates of the formation of CO2 and H2O ices in different environments. In addition, we study how chemistry is affected by the presence/absence of ice mantles (bare dust or icy dust) and the impact of considering different desorption probabilities. Conclusions: The type of substrate (bare dust or icy dust) and the probability of desorption can significantly alter the chemistry occurring on grain surfaces, leading to differences of several orders of magnitude in the abundances of gas-phase species, such as CO, H2CO, and CH3OH. The type of substrate, together with the density and intensity of the radiation field, also determine the threshold extinction to form ices of CO2 and H2O. We also conclude that H2CO and CH3OH are mainly released into the gas phase of low, far-ultraviolet illuminated PDRs through chemical desorption upon two-body surface reactions, rather than through photodesorption.

Improved Thermal Modulator for Gas Chromatography

NASA Technical Reports Server (NTRS)

Hasselbrink, Ernest Frederick, Jr.; Hunt, Patrick J.; Sacks, Richard D.

2008-01-01

An improved thermal modulator has been invented for use in a variant of gas chromatography (GC). The variant in question denoted as two-dimensional gas chromatography (2DGC) or GC-GC involves the use of three series-connected chromatographic columns, in the form of capillary tubes coated interiorly with suitable stationary phases (compounds for which different analytes exhibit different degrees of affinity). The two end columns are relatively long and are used as standard GC columns. The thermal modulator includes the middle column, which is relatively short and is not used as a standard GC column: instead, its temperature is modulated to affect timed adsorption and desorption of analyte gases between the two end columns in accordance with a 2DGC protocol.

Laser heating of scanning probe tips for thermal near-field spectroscopy and imaging

NASA Astrophysics Data System (ADS)

O'Callahan, Brian T.; Raschke, Markus B.

2017-02-01

Spectroscopy and microscopy of the thermal near-field yield valuable insight into the mechanisms of resonant near-field heat transfer and Casimir and Casimir-Polder forces, as well as providing nanoscale spatial resolution for infrared vibrational spectroscopy. A heated scanning probe tip brought close to a sample surface can excite and probe the thermal near-field. Typically, tip temperature control is provided by resistive heating of the tip cantilever. However, this requires specialized tips with limited temperature range and temporal response. By focusing laser radiation onto AFM cantilevers, we achieve heating up to ˜1800 K, with millisecond thermal response time. We demonstrate application to thermal infrared near-field spectroscopy (TINS) by acquiring near-field spectra of the vibrational resonances of silicon carbide, hexagonal boron nitride, and polytetrafluoroethylene. We discuss the thermal response as a function of the incident excitation laser power and model the dominant cooling contributions. Our results provide a basis for laser heating as a viable approach for TINS, nanoscale thermal transport measurements, and thermal desorption nano-spectroscopy.

Waste isolation safety assessment program. Task 4. Third contractor information meeting

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1980-06-01

The Contractor Information Meeting (October 14 to 17, 1979) was part of the FY-1979 effort of Task 4 of the Waste Isolation Safety Assessment Program (WISAP): Sorption/Desorption Analysis. The objectives of this task are to: evaluate sorption/desorption measurement methods and develop a standardized measurement procedure; produce a generic data bank of nuclide-geologic interactions using a wide variety of geologic media and groundwaters; perform statistical analysis and synthesis of these data; perform validation studies to compare short-term laboratory studies to long-term in situ behavior; develop a fundamental understanding of sorption/desorption processes; produce x-ray and gamma-emitting isotopes suitable for the study ofmore » actinides at tracer concentrations; disseminate resulting information to the international technical community; and provide input data support for repository safety assessment. Conference participants included those subcontracted to WISAP Task 4, representatives and independent subcontractors to the Office of Nuclear Waste Isolation, representatives from other waste disposal programs, and experts in the area of waste/geologic media interaction. Since the meeting, WISAP has been divided into two programs: Assessment of Effectiveness of Geologic Isolation Systems (AEGIS) (modeling efforts) and Waste/Rock Interactions Technology (WRIT) (experimental work). The WRIT program encompasses the work conducted under Task 4. This report contains the information presented at the Task 4, Third Contractor Information Meeting. Technical Reports from the subcontractors, as well as Pacific Northwest Laboratory (PNL), are provided along with transcripts of the question-and-answer sessions. The agenda and abstracts of the presentations are also included. Appendix A is a list of the participants. Appendix B gives an overview of the WRIT program and details the WRIT work breakdown structure for 1980.« less

Chemical desorption and diffusive dust chemistry

NASA Astrophysics Data System (ADS)

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

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

Determination of short chain chlorinated paraffins in water by stir bar sorptive extraction-thermal desorption-gas chromatography-triple quadrupole tandem mass spectrometry.

PubMed

Tölgyessy, P; Nagyová, S; Sládkovičová, M

2017-04-21

A simple, robust, sensitive and environment friendly method for the determination of short chain chlorinated paraffins (SCCPs) in water using stir bar sorptive extraction (SBSE) coupled to thermal desorption-gas chromatography-triple quadrupole tandem mass spectrometry (TD-GC-QqQ-MS/MS) was developed. SBSE was performed using 100mL of water sample, 20mL of methanol as a modifier, and a commercial sorptive stir bar (with 10mm×0.5mm PDMS layer) during extraction period of 16h. After extraction, the sorptive stir bar was thermally desorbed and online analysed by GC-MS/MS. Method performance was evaluated for MilliQ and surface water spiked samples. For both types of matrices, a linear dynamic range of 0.5-3.0μgL -1 with correlation coefficients >0.999 and relative standard deviations (RSDs) of the relative response factors (RRFs) <12% was established. The limits of quantification (LOQs) of 0.06 and 0.08μgL -1 , and the precision (repeatability) of 6.4 and 7.7% (RSDs) were achieved for MilliQ and surface water, respectively. The method also showed good robustness, recovery and accuracy. The obtained performance characteristics indicate that the method is suitable for screening and monitoring and compliance checking with environmental quality standards (EQS, set by the EU) for SCCPs in surface waters. Copyright © 2017 Elsevier B.V. All rights reserved.

a Thermally Desorbable Miniature Passive Dosimeter for Organic Vapors

NASA Astrophysics Data System (ADS)

Gonzalez, Jesus Antonio

A thermally desorbable miniature passive dosimeter (MPD) for organic vapors has been developed in conformity with theoretical and practical aspects of passive dosimeter design. The device was optimized for low sample loadings resulting from short-term and/or low concentration level exposure. This was accomplished by the use of thermal desorption rather than solvent elution, which provided the GC method with significantly higher sensitivity. Laboratory evaluation of this device for factors critical to the performance of passive dosimeters using benzene as the test vapor included: desorption efficiency (97.2%), capacity (1400 ppm-min), sensitivity (7ng/sample or 0.06 ppmv for 15 minutes sampling) accuracy and precision, concentration level, environmental conditions (i.e., air face velocity, relative humidity) and sample stability during short (15 minutes) and long periods of time (15 days). This device has demonstrated that its overall accuracy meets NIOSH and OSHA requirements for a sampling and analytical method for the exposure concentration range of 0.1 to 50 ppm (v/v) and 15 minutes exposures. It was demonstrated that the MPD operates in accordance with theoretically predicted performance and should be adequate for short-term and/or low concentration exposure monitoring of organic vapors in the workplace. In addition a dynamic vapor exposure evaluation system for passive dosimeters have been validated using benzene as the test vapor. The system is capable of generating well defined short-square wave concentration profiles suitable for the evaluation of passive dosimeters for ceiling exposure monitoring.

Characterization of diesel particles: effects of fuel reformulation, exhaust aftertreatment, and engine operation on particle carbon composition and volatility.

PubMed

Alander, Timo J A; Leskinen, Ari P; Raunemaa, Taisto M; Rantanen, Leena

2004-05-01

Diesel exhaust particles are the major constituent of urban carbonaceous aerosol being linked to a large range of adverse environmental and health effects. In this work, the effects of fuel reformulation, oxidation catalyst, engine type, and engine operation parameters on diesel particle emission characteristics were investigated. Particle emissions from an indirect injection (IDI) and a direct injection (DI) engine car operating under steady-state conditions with a reformulated low-sulfur, low-aromatic fuel and a standard-grade fuel were analyzed. Organic (OC) and elemental (EC) carbon fractions of the particles were quantified by a thermal-optical transmission analysis method and particle size distributions measured with a scanning mobility particle sizer (SMPS). The particle volatility characteristics were studied with a configuration that consisted of a thermal desorption unit and an SMPS. In addition, the volatility of size-selected particles was determined with a tandem differential mobility analyzer technique. The reformulated fuel was found to produce 10-40% less particulate carbon mass compared to the standard fuel. On the basis of the carbon analysis, the organic carbon contributed 27-61% to the carbon mass of the IDI engine particle emissions, depending on the fuel and engine operation parameters. The fuel reformulation reduced the particulate organic carbon emissions by 10-55%. In the particles of the DI engine, the organic carbon contributed 14-26% to the total carbon emissions, the advanced engine technology, and the oxidation catalyst, thus reducing the OC/EC ratio of particles considerably. A relatively good consistency between the particulate organic fraction quantified with the thermal optical method and the volatile fraction measured with the thermal desorption unit and SMPS was found.

Hard versus soft dynamics for adsorption-desorption kinetics: Exact results in one-dimension.

PubMed

Manzi, S J; Huespe, V J; Belardinelli, R E; Pereyra, V D

2009-11-01

The adsorption-desorption kinetics is discussed in the framework of the kinetic lattice-gas model. The master equation formalism has been introduced to describe the evolution of the system, where the transition probabilities are written as an expansion of the occupation configurations of all neighboring sites. Since the detailed balance principle determines half of the coefficients that arise from the expansion, it is necessary to introduce ad hoc, a dynamic scheme to get the rest of them. Three schemes of the so-called hard dynamics, in which the probability of transition from single site cannot be factored into a part which depends only on the interaction energy and one that only depends on the field energy, and five schemes of the so-called soft dynamics, in which this factorization is possible, were introduced for this purpose. It is observed that for the hard dynamic schemes, the equilibrium and nonequilibrium observables, such as adsorption isotherms, sticking coefficients, and thermal desorption spectra, have a normal or physical sustainable behavior. While for the soft dynamics schemes, with the exception of the transition state theory, the equilibrium and nonequilibrium observables have several problems. Some of them can be regarded as abnormal behavior.

(100) facets of γ-Al2O3: the active surfaces for alcohol dehydration reactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kwak, Ja Hun; Mei, Donghai; Peden, Charles HF

2011-05-01

Temperature programmed desorption (TPD) of ethanol, and methanol dehydration reaction were studied on γ-Al2O3 in order to identify the catalytic active sites for alcohol dehydration reactions. Two high temperature (> 473 K) desorption features were observed following ethanol adsorption. Samples calcined at T≤473 K displayed a desorption feature in the 523-533 K temperature range, while those calcined at T ≥ 673 K showed a single desorption feature at 498 K. The switch from the high to low temperature ethanol desorption correlated well with the dehydroxylation of the (100) facets of γ-Al2O3 that was predicted at 550 K DFT calculations. Theoreticalmore » DFT simulations of the mechanism of dehydration. on clean and hydroxylated γ-Al2O3(100) surfaces, find that a concerted elimination of ethylene from an ethanol molecule chemisorbed at an Al3+ pentacoordinated site is the rate limiting step for catalytic cycle on both surfaces. Furthermore, titration of the pentacoordinate Al3+ sites on the (100) facets of γ-Al2O3 by BaO completely turned off the methanol dehydration reaction activity. These results unambiguously demonstrate that only the (100) facets on γ-Al2O3 are the catalytic active surfaces for alcohol dehydration.« less

Interactions on External MOF Surfaces: Desorption of Water and Ethanol from CuBDC Nanosheets.

PubMed

Elder, Alexander C; Aleksandrov, Alexandr B; Nair, Sankar; Orlando, Thomas M

2017-10-03

The external surfaces of metal-organic framework (MOF) materials are difficult to experimentally isolate due to the high porosities of these materials. MOF surface surrogates in the form of copper benzenedicarboxylate (CuBDC) nanosheets were synthesized using a bottom-up approach, and the surface interactions of water and ethanol were investigated by temperature-programmed desorption (TPD). A method of analysis of diffusion-influenced TPD was developed to measure the desorption properties of these porous materials. This approach also allows the extraction of diffusion coefficients from TPD data. The transmission Fourier transform infrared spectra, powder X-ray diffraction patterns, and TPD data indicate that water desorbs from CuBDC nanosheets with activation energies of 44 ± 2 kJ/mol at edge sites and 58 ± 1 kJ/mol at external surface and internal and pore sites. Ethanol desorbs with activation energies of 58 ± 1 kJ/mol at internal pore sites and 66 ± 0.4 kJ/mol at external surface sites. Co-adsorption of water and ethanol was also investigated. The presence of ethanol was found to inhibit the desorption of water, resulting in a water desorption process with an activation energy of 68 ± 0.7 kJ/mol.

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.

Effect of Temperature on the Desorption of Lithium from Molybdenum(110) Surfaces: Implications for Fusion Reactor First Wall Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Mohan; Roszell, John; Scoullos, Emanuel V.

2016-03-30

Determining the strength of Li binding to Mo is critical to assessing the survivability of Li as a potential first wall material in fusion reactors. Here, we present the results of a joint experimental and theoretical investigation into how Li desorbs from Mo(110) surfaces, based on what can be deduced from temperature-programmed desorption measurements and density functional theory (DFT). Li desorption peaks measured at temperatures ranging from 711 K (1 monolayer, ML) to 1030 K (0.04 ML), with corresponding desorption onsets from 489 to 878 K, follow a trend similar to predicted Gibbs free energies for Li adsorption. Bader chargemore » analysis of DFT densities reveals that repulsive forces between neighboring positively charged Li atoms increase with coverage and thus reduce the bond strength between Mo and Li, thereby lowering the desorption temperature as the coverage increases. In addition, DFT predicts that Li desorbs at higher temperatures from a surface with vacancies than from a perfect surface, offering an explanation for the anomalously high desorption temperatures for the last Li to desorb from Mo(110). Analysis of simulated local densities of states indicates that the stronger binding to the defective surface is correlated with enhanced interaction between Li and Mo, involving the Li 2s electrons and not only the Mo 4d electrons as in the case of the pristine surface, but also the Mo 5s electrons in the case with surface vacancies. We suggest that steps and kinks present on the Mo(110) surface behave similarly and contribute to the high desorption temperatures. These findings imply that roughened Mo surfaces may strengthen Li film adhesion at higher temperatures.« less

Probing Atomic, Electronic, and Optical Structures of Nanoparticle Photocatalysts Using Fast Electrons

NASA Astrophysics Data System (ADS)

Liu, Qianlang

Graphene has attracted great interest in many fields due to its outstanding electronic and chemical properties. Among them, its surface inertness and high thermal stability makes graphene a promising candidate as a protective material for transition metal surfaces. Recent studies show, however, that small molecules, such as O2, CO and H2O, intercalate between a graphene film and a metal substrate at particular temperatures. The intercalation of O2 between graphene and Ru(0001) is studied with 3 keV helium ion scattering and low energy electron diffraction. It is shown that O2 intercalates between the graphene and the Ru(0001) substrate at a temperature of 650 K and does not adsorb onto the graphene surface. Nevertheless, the graphene layer efficiently avoids both intercalation and adsorption of oxygen at room temperature. It is also found that the intercalated oxygen thermally desorbs from the surface after it is heated to 800 K. Such a desorption is not, however, observed for oxygen dissociatively adsorbed on a bare Ru(0001) surface until 1200 K. It is thus inferred that the oxygen intercalated between graphene and Ru(0001) is in a molecular form. In addition, part of the graphene overlayer is etched by a chemical reaction during the thermal desorption of oxygen. The role of the defects on the graphene layer is also studied. Defects are introduced by 50 eV Ar+ sputtering, which creates single vacancies with a quick sputtering or larger open areas of substrate following a prolonged sputtering. It is found that oxygen molecularly adsorbs at single carbon vacancies even at room temperature, which does not occur on a complete graphene layer. Following post-annealing to 600 K, it is observed that such adsorbed oxygen diffuses to become intercalated between graphene and Ru(0001). Oxygen dissociatively adsorbs in the large open areas of exposed substrate by forming strong oxygen-metal bonds. It is also found that the presence of defects facilitates the intercalation of oxygen and improves the etching efficiency of the graphene during the desorption of oxygen.

The preparation and hydrogen brittleness resistance of Pd71.5Cu12Si16.5 metallic glass ribbons

NASA Astrophysics Data System (ADS)

Du, Xiaoqing; Ye, Xiaoqiu; Ren, Qingbo

2017-12-01

Pd71.5Cu12Si16.5 metallic glass ribbons as wide as 10mm were prepared by splat quenching. Structure was identified with X-ray diffraction (XRD) spectrums from the conventional X-ray diffractometer and also short wavelength X-ray stress analyzer. The results confirm fully amorphous structure of the ribbons. Multiple H2 adsorption and desorption cycles under a pressure of 100kPa were carried out in the metallic glass ribbon and also pure palladium membrane for comparison. The former didn’t show any cracks after more than 10 cycles, and thermal desorption spectroscopy (TDS) measurement confirms that hydrogen was adsorbed abundantly in the metallic glass ribbon. Pd71.5Cu12Si16.5 metallic glass ribbons demonstrate excellent hydrogen brittleness resistance.

DEVELOPMENT OF A SYSTEMATIC APPROACH TO ...

EPA Pesticide Factsheets

Risk assessment is a crucial component of the site remediation decision-making process. Some current EPA methods do not have detection limits low enough for risk assessment of many VOCs (e.g., EPA Region 3 Risk Based Concentration levels, EPA Region 9 Preliminary Remediation Goals, state-specified concentration levels). The magnitude of this problem was described in a paper recently presented at a University of Massachusetts Remediation Conference with the conclusion that the resolution of this issue is critical for valid human health and ecological risk assessments. Likewise, the difficulty of obtaining complete extraction of water-soluble VOCs and semi-volatile organic compounds (SVOCs) makes the generation of reliable and reproducible data a serious concern in site characterization and risk assessment programs.This poster presents findings of the development of an analytical method which uses thermal desorption combined with dual gas chromatography/mass spectrometry (GC/MS) to extract and accurately measure low levels of VOCs and SVOCs in soil and sediment samples with medium to high moisture content. Thermal extraction was selected for examination because the technique is simpler and more efficient than the present EPA purge-and-trap methods, and all water-soluble compounds are amenable to the procedure. Efforts were made to modify commonly used instrumentation (e.g., Archon

Design of Zeolitic Imidazolate Framework Derived Nitrogen-Doped Nanoporous Carbons Containing Metal Species for Carbon Dioxide Fixation Reactions.

PubMed

Toyao, Takashi; Fujiwaki, Mika; Miyahara, Kenta; Kim, Tae-Ho; Horiuchi, Yu; Matsuoka, Masaya

2015-11-01

Various N-doped nanoporous carbons containing metal species were prepared by direct thermal conversion of zeolitic imidazolate frameworks (ZIFs; ZIF-7, -8, -9, and -67) at different temperatures (600, 800, and 1000 °C). These materials were utilized as bifunctional acid-base catalysts to promote the reaction of CO2 with epoxides to form cyclic carbonates under 0.6 MPa of CO2 at 80 °C. The catalyst generated by thermal conversion of ZIF-9 at 600 °C (C600-ZIF-9) was found to exhibit a higher catalytic activity than the other ZIFs, other conventional catalysts, and other metal-organic framework catalysts. The results of various characterization techniques including elemental analysis, X-ray diffraction, X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and transmission electron microscopy show that C600-ZIF-9 contains partly oxidized Co nanoparticles and N species. Temperature-programmed desorption measurements by using CO2 and NH3 as probe molecules revealed that C600-ZIF-9 has both Lewis acid and Lewis base catalytic sites. Finally, the substrate scope was extended to seven other kinds of epoxides. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fields, J. D.; Gedvilas, L.; Kiriluk, K.

Deep oxygen related defects form in hydrogenated nanocrystalline silicon (nc-Si:H) as a consequence of thermal annealing, but their microscopic origins and formation mechanisms are not well understood. To gain insight to this behavior we intentionally drive-out hydrogen from nc-Si:H films by thermal annealing and monitor accompanying changes in the electronic and vibrational structure of the films with photoluminescence (PL) and Fourier transform infrared (FTIR) absorption spectroscopy. Hydrogen effusion (HE) data provide additional insight, because the annealing temperature range shown to induce a defect band, centered at {approx}0.7 eV in PL studies, and that corresponding to the onset of thermally activatedmore » hydrogen desorption from grain boundaries, coincide. This coincidence suggests a probable link between the two processes. The activation energy obtained from correlated annealing-PL experiments, of {approx}0.6 eV, for defect formation with thermal exposure, provides substantial insight regarding the mechanism.« less

Method and apparatus for thermal swing adsorption and thermally-enhanced pressure swing adsorption

DOEpatents

Wegeng, Robert S.; Rassat, Scot D.; TeGrotenhuis, Ward E.; Drost, Kevin; Vishwanathan, Vilayanur V.

2004-06-08

The present invention provides compact adsorption systems that are capable of rapid temperature swings and rapid cycling. Novel methods of thermal swing adsorption and thermally-enhanced pressure swing adsorption are also described. In some aspects of the invention, a gas is passed through the adsorbent thus allowing heat exchangers to be very close to all portions of the adsorbent and utilize less space. In another aspect, the adsorption media is selectively heated, thus reducing energy costs. Methods and systems for gas adsorption/desorption having improved energy efficiency with capability of short cycle times are also described. In another aspect, the apparatus or methods utilize heat exchange channels of varying lengths that have volumes controlled to provide equal heat fluxes. Methods of fuel cell startup are also described. Advantages of the invention include the ability to use (typically) 30-100 times less adsorbent compared to conventional systems.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shiozawa, Yuichiro; Koitaya, Takanori; Mukai, Kozo

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 atmore » 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.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, R. Scott; Li, Zhenjun; Chen, Long

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 occupymore » 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.« less

On-line gas chromatographic analysis of airborne particles

DOEpatents

Hering, Susanne V [Berkeley, CA; Goldstein, Allen H [Orinda, CA

2012-01-03

A method and apparatus for the in-situ, chemical analysis of an aerosol. The method may include the steps of: collecting an aerosol; thermally desorbing the aerosol into a carrier gas to provide desorbed aerosol material; transporting the desorbed aerosol material onto the head of a gas chromatography column; analyzing the aerosol material using a gas chromatograph, and quantizing the aerosol material as it evolves from the gas chromatography column. The apparatus includes a collection and thermal desorption cell, a gas chromatograph including a gas chromatography column, heated transport lines coupling the cell and the column; and a quantization detector for aerosol material evolving from the gas chromatography column.

Chemistry of CCl 4 on Fe 3O 4(1 1 1)-(2 × 2) surfaces in the presence of adsorbed D 2O studied by temperature programmed desorption

NASA Astrophysics Data System (ADS)

Adib, K.; Totir, G. G.; Fitts, J. P.; Rim, K. T.; Mueller, T.; Flynn, G. W.; Joyce, S. A.; Osgood, R. M.

2003-07-01

Temperature programmed desorption (TPD) was used to study surface reactions of Fe 3O 4(1 1 1)-(2 × 2) sequentially exposed, at ˜100 K, to vapor-phase D 2O and CCl 4. Previous TPD and XPS results have indicated that in the absence of D 2O, CCl 4 dissociatively adsorbs on Fe 3O 4(1 1 1) producing chemisorbed Cl and CCl 2. Subsequent heating of the surface results in abstraction of lattice iron and oxygen atoms and causes them to desorb as FeCl 2 and OCCl 2, respectively. This study shows that when this Fe 3O 4 surface is exposed only to D 2O, TPD measures a rich surface chemistry with multiple desorption events extending as high as ˜800 K, indicating dissociative adsorption of D 2O on the Fe 3O 4(1 1 1) surface. After sequential exposure to D 2O and then CCl 4, the production of FeCl 2 and OCCl 2 from adsorbed CCl 4 is suppressed, indicating that D 2O fragments block the surface reactive sites.

Surface diffusion of In on Ge(111) studied by optical second harmonic microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Suni, I.I.; Seebauer, E.G.

Surface diffusion of In on Ge(111) has been measured by optical second harmonic microscopy. This technique employs surface second harmonic generation to directly image submonolayer surface concentration profiles. The coverage dependence of the diffusivity [ital D] can then be obtained from a Boltzmann--Matano analysis. In the coverage range 0.1[lt][theta][lt]0.48, the activation energy [ital E][sub diff] decreased with increasing coverage, ranging from 31 kcal/mol at [theta]=0.1 to 23 kcal/mol at [theta]=0.48. Over the same coverage range, the pre-exponential factor [ital D][sub 0] decreased from 5[times]10[sup 2] to 1[times]10[sup [minus]1] cm[sup 2]/s. This gradual change reflects a change in diffusion mechanism arisingmore » from the disordered nature of the Ge(111) surface. At low coverages, In adatoms sink into the top layer of Ge, and diffusion is dominated by thermal formation of adatom-vacancy pairs. At high coverages, diffusion occurs by normal site-to-site hopping. The gradual change in diffusion parameters with coverage was interrupted by an apparent phase transition at [theta]=0.16. At this point, both [ital E][sub diff] and [ital D][sub 0] peaked sharply at 41 kcal/mol and 6[times]10[sup 5] cm[sup 2]/s, respectively. The desorption energy [ital E][sub des] was measured by temperature programmed desorption. [ital E][sub des] decreased from 60 kcal/mol at submonolayer coverages to 55 kcal/mol at multilayer coverages.« less

Dispersion measurement by the single introduction method coupled with the back-sorption procedure: A chemisorption and TPD study of the different chemisorbed hydrogen species

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ragaini, V.; Giannantonio, R.; Magni, P.

1994-03-01

The Single Introduction (S.I.) method for the measurement by hydrogen chemisorption of metal dispersion in supported metal catalysts has been tested on two commercial 5% Pd/Al[sub 2]O[sub 3] catalysts. The S.I. results are compared with those obtained by the classical method of determining the adsorption isotherm (i.e., the multiple introduction method) and by O[sub 2]/H[sub 2] titration. As in Part I of this work, both chemisorption and thermal desorption have been used to find the best experimental conditions for the [open quotes]Back-Sorption[close quotes] procedure. It is shown that [alpha]- and [beta]-palladium hydrides can be decomposed by outgassing the samples formore » less than 5 min at 305 K and 10[sup [minus]6] Torr and that 30 min pumping at the same temperature and pressure is sufficient to eliminate from the catalyst surface the weakly adsorbed hydrogen as well. It has also been verified that chemisorption of hydrogen on these catalysts at room temperature is complete at pressures lower than those required for the [alpha] [yields] [beta] phase transition, so that it is possible to perform dispersion measurements by means of a simple S.I. of hydrogen coupled with Back-Sorption below 15 Torr at 305 K. Temperature-programmed desorption of hydrogen on one of the samples outlines the need to discriminate among the different adsorbed species for a more detailed characterization of supported metal catalysts. 44 refs., 10 figs., 2 tabs.« less

Report on the deuterium retention in CVD coated W on SiC in support of the Ultramet Company’s Small Business Innovation Research (SBIR) project: SOW DE-FG02-07ER84941

DOE Office of Scientific and Technical Information (OSTI.GOV)

Masashi Shimada

2012-06-01

A tungsten (W) coated (0.0005-inch thickness) silicon carbide (SiC) (1.0-inch diameter and 0.19-inch thickness) sample was exposed to a divertor relevant high-flux (~1022 m-2s-1) deuterium plasma at 200 and 400°C in the Idaho National Laboratory’s (INL’s) Tritium Plasma Experiment (TPE), and the total deuterium retention was subsequently measured via the thermal desorption spectroscopy (TDS) method. The deuterium retentions were 6.4x1019 m-2 and 1.7x1020 m-2, for 200 and 400°C exposure, respectively. The Tritium Migration Analysis Program (TMAP) was used to analyze the measured TDS spectrum to investigate the deuterium behavior in the W coated SiC, and the results indicated that mostmore » of the deuterium was trapped in the W coated layer even at 400°C. This thin W layer (0.0005-inch ~ 13µm thickness) prevented deuterium ions from bombarding directly into the SiC substrate, minimizing erosion of SiC and damage creation via ion bombardment. The shift in the D desorption peak in the TDS spectra from 200 C to 400°C can be attributed to D migration to the bulk material. This unexpectedly low deuterium retention and short migration might be due to the porous nature of the tungsten coating, which can decrease the solution concentration of deuterium atoms.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petrik, Nikolay G.; Henderson, Michael A.; Kimmel, Gregory A.

Angle-resolved photon stimulated desorption (PSD) combined with infrared reflection-adsorption spectroscopy and temperature programmed desorption reveal two distinct channels in the photochemistry of acetone on rutile TiO₂(110) surface. During UV irradiation of co-adsorbed oxygen and acetone molecules, methyl radicals (CH₃) are ejected in two different directions: i) normal to the surface and ii) off-normal at ~±66° to the surface normal in the azimuth (i.e. perpendicular to the rows of bridging oxygen and Ti atoms). Both components are relatively narrow and non-cosine, indicating non-thermal evolution of CH₃ radicals. The direction of the “off-normal” PSD component is consistent with orientation of the C–CH₃more » bonds in the n²-acetone diolate—a photoactive form of acetone chemisorption on the oxidized TiO₂(110) surface proposed earlier from experimental and theoretical studies. The direction of the “normal” PSD component requires an orientation of a C–CH₃ bond which is not consistent with the n²-acetone diolate structure. The angular distribution of the CH₃ PSD depends on the acetone coverage. The “off-normal” PSD component dominates at lower acetone coverage (< 0.2 ML), but does not increase at higher coverages in accord with the acetone diolate peak intensity in the infrared reflection-absorption spectra. The “normal” PSD component grows with the acetone coverage up to 0.6 ML. The newly discovered “normal” PSD channel is tentatively assigned to a photo-produced n²- acetone enolate as a potential precursor based on the H/D exchange experiments« less

A Comparative Study of Hydrodeoxygenation of Furfural Over Fe/Pt(111) and Fe/Mo 2C Surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wan, Weiming; Jiang, Zhifeng; Chen, Jingguang G.

It is desirable to convert biomass-derived furfural to 2-methylfuran through the hydrodeoxygenation (HDO) reaction using an inexpensive catalyst with high stability. In this work, Mo 2C was used as an alternative substrate to replace precious Pt to support monolayer Fe for the HDO reaction of furfural. The HDO activity and stability of Fe/Pt(111) and Fe/Mo 2C/Mo(110) surfaces were compared. Density functional theory calculations and vibrational spectroscopy results indicated that both surfaces bonded to furfural with similar adsorption geometries and should be active toward the furfural HDO reaction. Temperature programmed desorption experiments confirmed a similar HDO activity between the two surfaces,more » with Fe/Mo 2C/Mo(110) being more thermally stable than Fe/Pt(111). As a result, the combined theoretical and experimental results demonstrated that Fe/Mo 2C should be a promising non-precious metal catalyst for the HDO reaction of furfural to produce 2-methylfuran.« less

A Comparative Study of Hydrodeoxygenation of Furfural Over Fe/Pt(111) and Fe/Mo 2C Surfaces

DOE PAGES

Wan, Weiming; Jiang, Zhifeng; Chen, Jingguang G.

2018-01-19

It is desirable to convert biomass-derived furfural to 2-methylfuran through the hydrodeoxygenation (HDO) reaction using an inexpensive catalyst with high stability. In this work, Mo 2C was used as an alternative substrate to replace precious Pt to support monolayer Fe for the HDO reaction of furfural. The HDO activity and stability of Fe/Pt(111) and Fe/Mo 2C/Mo(110) surfaces were compared. Density functional theory calculations and vibrational spectroscopy results indicated that both surfaces bonded to furfural with similar adsorption geometries and should be active toward the furfural HDO reaction. Temperature programmed desorption experiments confirmed a similar HDO activity between the two surfaces,more » with Fe/Mo 2C/Mo(110) being more thermally stable than Fe/Pt(111). As a result, the combined theoretical and experimental results demonstrated that Fe/Mo 2C should be a promising non-precious metal catalyst for the HDO reaction of furfural to produce 2-methylfuran.« less

Reverse Aging of Composite Materials for Aeronautical Applications

NASA Astrophysics Data System (ADS)

lannone, Michele

2008-08-01

Hygro-thermal ageing of polymer matrix composite materials is a major issue for all the aeronautical structures. For carbon-epoxy composites generally used in aeronautical applications the major effect of ageing is the humidity absorption, which induces a plasticization effect, generally decreasing Tg and elastic moduli, and finally design allowables. A thermodynamical and kinetic study has been performed, aimed to establish a program of periodic heating of the composite part, able to reversing the ageing effect by inducing water desorption. The study was founded on a simple model based on Fick's law, coupled with a concept of "relative saturation coefficient" depending on the different temperature of the composite part and the environment. The behaviour of some structures exposed to humidity and "reverse aged" by heating has been virtually tested. The conclusion of the study allowed to issue a specific patent application for aeronautical structures to be designed on the basis of a "humidity free" concept which allows the use of higher design allowables; having as final results lighter composite structures with a simplified certification process.

The effect of high energy ion beam analysis on D trapping in W

NASA Astrophysics Data System (ADS)

Finlay, T. J.; Davis, J. W.; Schwarz-Selinger, T.; Haasz, A. A.

2017-12-01

High energy ion beam analyses (IBA) are invaluable for measuring concentration depth profiles of light elements in solid materials, and important in the study of fusion fuel retention in tokamaks. Polycrystalline W specimens were implanted at 300 and 500 K, 5-10 × 1023 D m-2 fluence, with deuterium-only and simultaneous D-3%He ion beams. Selected specimens were analysed by elastic recoil detection analysis (ERDA) and/or nuclear reaction analysis (NRA). All specimens were measured by thermal desorption spectroscopy (TDS). The D TDS spectra show an extra peak at 900-1000 K following ERDA and/or NRA measurements. The peak height appears to correlate with the amount of D initially trapped beyond the calculated IBA probe beam peak damage depth. Similar to pre-implantation damage scenarios, the IBA probe beam creates empty high energy traps which later retrap D atoms during TDS heating, which is supported by modelling experimental results using the Tritium Migration Analysis Program.

New Ni-based quaternary disk-shaped catalysts for low-temperature CO2 methanation: Fabrication, characterization, and performance.

PubMed

Moon, Dea Hyun; Lee, Sang Moon; Ahn, Jeong Yoon; Nguyen, Dinh Duc; Kim, Sung Su; Chang, Soon Woong

2018-07-15

Ni-based quaternary disk catalysts were manufactured for low-temperature CO 2 methanation reactions, and the reaction activity was examined with respect to the thermal treatment conditions. By applying varying reduction and combustion treatments, the same catalysts were compared, and the Ni oxidation conditions and physical features were confirmed through X-Ray diffraction, scanning electron microscopy, and energy dispersive X-ray analyses. In addition, oxygen adsorption/desorption changes were measured by temperature-programmed reduction after pre-treating with oxygen and hydrogen. The reduction treatment catalyst showed a conversion of 20% at 280 °C, and the 70% calcined catalyst did not form a NiO crystalloid. The activation of the catalyst increased because of NiO movement on the catalyst surface, which enabled easy transformation to metallic Ni. The prepared catalyst is a highly reactive, yet stable, candidate for practical catalytic CO 2 methanation. Copyright © 2018 Elsevier Ltd. All rights reserved.

Effects of temperature and surface contamination on D retention in ultrathin Li films on TZM

DOE PAGES

Capece, A. M.; Roszell, J. P.; Skinner, C. H.; ...

2014-10-29

Here in this work, we investigate deuterium retention at the Mo-Li interface by studying thin Li films three monolayers thick on a TZM Mo alloy. Li films at temperatures between 315 and 460 K were exposed to a deuterium ion beam and D retention was measured using temperature programmed desorption. In the absence of oxygen, D is retained as LiD, and the relative amount of retained D decreases with increasing substrate temperature. In three-monolayer thick lithium oxide films, the amount of D retained was 2.5 times higher than the amount retained as LiD in the metallic Li film. However, oxygenmore » reduces the thermal stability of D in the film, causing D 2O and D 2 to be released from the surface at temperatures 150-200 K below the LiD decomposition temperature. These results highlight the importance of maintaining a metallic Li layer for high D retention in Li films on TZM at elevated temperatures.« less

An Overview of INEL Fusion Safety R&D Facilities

NASA Astrophysics Data System (ADS)

McCarthy, K. A.; Smolik, G. R.; Anderl, R. A.; Carmack, W. J.; Longhurst, G. R.

1997-06-01

The Fusion Safety Program at the Idaho National Engineering Laboratory has the lead for fusion safety work in the United States. Over the years, we have developed several experimental facilities to provide data for fusion reactor safety analyses. We now have four major experimental facilities that provide data for use in safety assessments. The Steam-Reactivity Measurement System measures hydrogen generation rates and tritium mobilization rates in high-temperature (up to 1200°C) fusion relevant materials exposed to steam. The Volatilization of Activation Product Oxides Reactor Facility provides information on mobilization and transport and chemical reactivity of fusion relevant materials at high temperature (up to 1200°C) in an oxidizing environment (air or steam). The Fusion Aerosol Source Test Facility is a scaled-up version of VAPOR. The ion-implanta-tion/thermal-desorption system is dedicated to research into processes and phenomena associated with the interaction of hydrogen isotopes with fusion materials. In this paper we describe the capabilities of these facilities.

Metal-support interactions during the adsorption of CO on thin layers and islands of epitaxial palladium

NASA Technical Reports Server (NTRS)

Park, C.; Poppa, H.; Soria, F.

1984-01-01

Islands and continuous layers of palladium were grown in an ultrahigh vacuum on substrates of Mo(110)c(14 x 7)-O, designated MoO(x), and of clean Mo(110). It was found that as-deposited islands and layers exhibited bulk palladium adsorption properties for CO when deposited at room temperature and for palladium thicknesses in excess of about 3 monolayers. CO adsorption was drastically reduced, however, on annealing. For islands, annealing temperatures of as low as 400 K led to some reduction in CO adsorption whereas more severe reductions were found to occur at 600 K for islands and at 800 K for continuous multilayers. The deactivation depended on the palladium thickness, the substrate species and the extent of thermal treatments. Auger electron spectroscopy, temperature-programmed desorption and Delta-Phi measurements were combined to interpret the deactivation behavior in terms of substrate-support interactions involving the diffusion of substrate species towards the palladium surface.

Synthesis of Dicyclopentadiene Oligomer Over Nanoporous Al-MCM-41 Catalysts.

PubMed

Park, Eunseo; Kim, Jinhan; Yim, Jin-Heong; Han, Jeongsik; Kwon, Tae Soo; Park, Y K; Jeon, Jong-Ki

2016-05-01

One step reaction composed of DCPD oligomerization and DCPD oligomer isomerization was investigated over nanoporous Al-MCM-41 catalysts. The effects of aluminum grafting over MCM-41 on the catalyst characteristics were studied with respect to the synthesis of TCPD isomer. Physical and chemical properties of the catalysts were analyzed by N2 adsorption, temperature-programmed desorption of ammonia, and infrared spectroscopy of adsorbed pyridine. The overall number of acid sites as well as the number of Lewis acid sites increased with increasing of aluminum content over MCM-41. When utilizing MCM-41 and Al-MCM-41 as the catalyst, DCPD oligomerization reaction activity greatly increased compared to the thermal reaction. The highest TCPD isomer selectivity over the Al-MCM-41 catalyst with the highest aluminum content could be ascribed to the largest amount of acid sites. This study showed an increased level of TCPD isomer selectivity by an increasing level of Lewis acid sites through aluminum addition over MCM-41.

Effects of temperature and surface contamination on D retention in ultrathin Li films on TZM

DOE Office of Scientific and Technical Information (OSTI.GOV)

Capece, A. M.; Roszell, J. P.; Skinner, C. H.

Here in this work, we investigate deuterium retention at the Mo-Li interface by studying thin Li films three monolayers thick on a TZM Mo alloy. Li films at temperatures between 315 and 460 K were exposed to a deuterium ion beam and D retention was measured using temperature programmed desorption. In the absence of oxygen, D is retained as LiD, and the relative amount of retained D decreases with increasing substrate temperature. In three-monolayer thick lithium oxide films, the amount of D retained was 2.5 times higher than the amount retained as LiD in the metallic Li film. However, oxygenmore » reduces the thermal stability of D in the film, causing D 2O and D 2 to be released from the surface at temperatures 150-200 K below the LiD decomposition temperature. These results highlight the importance of maintaining a metallic Li layer for high D retention in Li films on TZM at elevated temperatures.« less

Volatile Organic Compound (VOC) profiling of Citrus tristeza virus (CTV) infection in sweet orange citrus varietals using thermal desorption gas chromatography time of flight mass spectrometry (TD-GC/TOF-MS)

USDA-ARS?s Scientific Manuscript database

Citrus tristeza virus (CTV) is a plant pathogen which predominately infects economically important citrus crops such as sweet orange, clementine, lime and grapefruit varietals. Within the last 70 years, an estimated 100 million citrus trees on sour orange rootstock have been destroyed due to CTV inf...

Measuring and predicting the emission rate of phthalate plasticizer from vinyl flooring in a specially-designed chamber.

PubMed

Xu, Ying; Liu, Zhe; Park, Jinsoo; Clausen, Per A; Benning, Jennifer L; Little, John C

2012-11-20

The emission of di-2-ethylhexyl phthalate (DEHP) from vinyl flooring (VF) was measured in specially designed stainless steel chambers. In duplicate chamber studies, the gas-phase concentration in the chamber increased slowly and reached a steady state level of 0.8-0.9 μg/m(3) after about 20 days. By increasing the area of vinyl flooring and decreasing that of the stainless steel surface within the chamber, the time to reach steady state was significantly reduced, compared to a previous study (1 month versus 5 months). The adsorption isotherm of DEHP on the stainless steel chamber surfaces was explicitly measured using solvent extraction and thermal desorption. The strong partitioning of DEHP onto the stainless steel surface was found to follow a simple linear relationship. Thermal desorption resulted in higher recovery than solvent extraction. Investigation of sorption kinetics showed that it takes several weeks for the sorption of DEHP onto the stainless steel surface to reach equilibrium. The content of DEHP in VF was measured at about 15% (w/w) using pressurized liquid extraction. The independently measured or calculated parameters were used to validate an SVOC emission model, with excellent agreement between model prediction and the observed gas-phase DEHP chamber concentrations.

Simple system for measuring tritium Ad/absorption using a 2. pi. counter and thermal desorption spectrometer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miyake, H.; Matsuyama, M.; Watanabe, K.

1992-03-01

In this paper, the authors develop a simple system using tritium tracer and thermal desorption techniques to measure the tritium adsorption and/or absorption on/in a material having typical surface conditions: namely, not cleaned surface. The tritium counting devices used were a 2{pi} counter and conventional proportional counter. With this system, the amounts of ad/absorption could be measured without exposing the samples to air after exposing them to tritium gas. The overall efficiency (F) of the 2{pi} counter was described at F = exp({minus}2.64h), where h is the distance from the sample to the detector. Ad/absorption measurements were carried out formore » several materials used for fabricating conventional vacuum systems. The results were, in the order of decreasing amounts of ad/absorption, as (fiber reinforced plastics(FRP)) {gt} (nickel(Ni), molybdenum disulfide(MoS{sub 2})) {gt} (stainless steel (SS304), iron(Fe), aluminum alloy(A2219)) {gt} (boron nitride(h-BN), silicon carbide (SiC), SS304 passivated by anodic oxidation layers(ASS) and that by boron nitride segregation layers (BSS)). The relative amounts were abut 100 for Ni and 0.1 for ASS and BSS, being normalized to Fe = 1.« less

Development of analysis of volatile polyfluorinated alkyl substances in indoor air using thermal desorption-gas chromatography-mass spectrometry.

PubMed

Wu, Yaoxing; Chang, Victor W-C

2012-05-18

The study attempts to utilize thermal desorption (TD) coupled with gas chromatography-mass spectrometry (GC-MS) for determination of indoor airborne volatile polyfluorinated alkyl substances (PFASs), including four fluorinated alcohols (FTOHs), two fluorooctane sulfonamides (FOSAs), and two fluorooctane sulfonamidoethanols (FOSEs). Standard stainless steel tubes of Tenax/Carbograph 1 TD were employed for low-volume sampling and exhibited minimal breakthrough of target analytes in sample collection. The method recoveries were in the range of 88-119% for FTOHs, 86-138% for FOSAs, exhibiting significant improvement compared with other existing air sampling methods. However, the widely reported high method recoveries of FOSEs were also observed (139-210%), which was probably due to the structural differences between FOSEs and internal standards. Method detection limit, repeatability, linearity, and accuracy were reported as well. The approach has been successfully applied to routine quantification of targeted PFASs in indoor environment of Singapore. The significantly shorter sampling time enabled the observation of variations of concentrations of targeted PFASs within different periods of a day, with higher concentration levels at night while ventilation systems were shut off. This indicated the existence of indoor sources and the importance of building ventilation and air conditioning system. Copyright © 2012 Elsevier B.V. All rights reserved.

A thermal extrapolation method for the effective temperatures and internal energies of activated ions

NASA Astrophysics Data System (ADS)

Meot-Ner (Mautner), Michael; Somogyi, Árpád

2007-11-01

The internal energies of dissociating ions, activated chemically or collisionally, can be estimated using the kinetics of thermal dissociation. The thermal Arrhenius parameters can be combined with the observed dissociation rate of the activated ions using kdiss = Athermalexp(-Ea,thermal/RTeff). This Arrhenius-type relation yields the effective temperature, Teff, at which the ions would dissociate thermally at the same rate, or yield the same product distributions, as the activated ions. In turn, Teff is used to calculate the internal energy of the ions and the energy deposited by the activation process. The method yields an energy deposition efficiency of 10% for a chemical ionization proton transfer reaction and 8-26% for the surface collisions of various peptide ions. Internal energies of ions activated by chemical ionization or by gas phase collisions, and of ions produced by desorption methods such as fast atom bombardment, can be also evaluated. Thermal extrapolation is especially useful for ion-molecule reaction products and for biological ions, where other methods to evaluate internal energies are laborious or unavailable.

Tortuous path chemical preconcentrator

DOEpatents

Manginell, Ronald P.; Lewis, Patrick R.; Adkins, Douglas R.; Wheeler, David R.; Simonson, Robert J.

2010-09-21

A non-planar, tortuous path chemical preconcentrator has a high internal surface area having a heatable sorptive coating that can be used to selectively collect and concentrate one or more chemical species of interest from a fluid stream that can be rapidly released as a concentrated plug into an analytical or microanalytical chain for separation and detection. The non-planar chemical preconcentrator comprises a sorptive support structure having a tortuous flow path. The tortuosity provides repeated twists, turns, and bends to the flow, thereby increasing the interfacial contact between sample fluid stream and the sorptive material. The tortuous path also provides more opportunities for desorption and readsorption of volatile species. Further, the thermal efficiency of the tortuous path chemical preconcentrator is comparable or superior to the prior non-planar chemical preconcentrator. Finally, the tortuosity can be varied in different directions to optimize flow rates during the adsorption and desorption phases of operation of the preconcentrator.

Integrated explosive preconcentrator and electrochemical detection system for 2,4,6-trinitrotoluene (TNT) vapor.

PubMed

Cizek, Karel; Prior, Chad; Thammakhet, Chongdee; Galik, Michal; Linker, Kevin; Tsui, Ray; Cagan, Avi; Wake, John; La Belle, Jeff; Wang, Joseph

2010-02-19

This article reports on an integrated explosive-preconcentration/electrochemical detection system for 2,4,6-trinitrotoluene (TNT) vapor. The challenges involved in such system integration are discussed. A hydrogel-coated screen-printed electrode is used for the detection of the thermally desorbed TNT from a preconcentration device using rapid square wave voltammetry. Optimization of the preconcentration system for desorption of TNT and subsequent electrochemical detection was conducted yielding a desorption temperature of 120 degrees C under a flow rate of 500 mL min(-1). Such conditions resulted in a characteristic electrochemical signal for TNT representing the multi-step reduction process. Quantitative measurements produced a linear signal dependence on TNT quantity exposed to the preconcentrator from 0.25 to 10 microg. Finally, the integrated device was successfully demonstrated using a sample of solid TNT located upstream of the preconcentrator. Copyright 2009 Elsevier B.V. All rights reserved.

Tungsten nitride coatings obtained by HiPIMS as plasma facing materials for fusion applications

NASA Astrophysics Data System (ADS)

Tiron, Vasile; Velicu, Ioana-Laura; Porosnicu, Corneliu; Burducea, Ion; Dinca, Paul; Malinský, Petr

2017-09-01

In this work, tungsten nitride coatings with nitrogen content in the range of 19-50 at% were prepared by reactive multi-pulse high power impulse magnetron sputtering as a function of the argon and nitrogen mixture and further exposed to a deuterium plasma jet. The elemental composition, morphological properties and physical structure of the samples were investigated by Rutherford backscattering spectrometry, atomic force microscopy and X-ray diffraction. Deuterium implantation was performed using a deuterium plasma jet and its retention in nitrogen containing tungsten films was investigated using thermal desorption spectrometry. Deuterium retention and release behaviour strongly depend on the nitrogen content in the coatings and the films microstructure. All nitride coatings have a polycrystalline structure and retain a lower deuterium level than the pure tungsten sample. Nitrogen content in the films acts as a diffusion barrier for deuterium and leads to a higher desorption temperature, therefore to a higher binding energy.

Facile synthesis of self-assembled biporous NiO and its electrochemical properties

NASA Astrophysics Data System (ADS)

Muruganandham, M.; Suri, Rominder P. S.; Sillanpää, Mika; Lee, Gang-Juan; Wu, Jerry J.

2016-09-01

In this article, we report the synthesis of self-assembled bi-porous nickel oxide on a large scale without using any templates or matrix. Porous NiO microspheres composed of particles were obtained by thermal decomposition of nickel oxalate, which was prepared using nickel salt and oxalic acid as precursors. The as-obtained nickel oxalate and nickel oxide were characterized using X-ray powder diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), X-ray Photoelectron Spectroscopy (XPS), thermogravimetric analysis (TGA), and nitrogen adsorption-desorption analysis. The influence of various experimental conditions on the formation nickel oxalate and NiO were studied. The nitrogen adsorption-desorption analysis showed that the synthesized NiO possesses a biporous (both mesoporous and macroporous) surface structur. The NiO microspheres showed a discharge capacity of 2929 mAh g-1. A plausible mechanism for the NiO self-assembly was proposed.

Optical absorption and oxygen passivation of surface states in III-nitride photonic devices

NASA Astrophysics Data System (ADS)

Rousseau, Ian; Callsen, Gordon; Jacopin, Gwénolé; Carlin, Jean-François; Butté, Raphaël; Grandjean, Nicolas

2018-03-01

III-nitride surface states are expected to impact high surface-to-volume ratio devices, such as nano- and micro-wire light-emitting diodes, transistors, and photonic integrated circuits. In this work, reversible photoinduced oxygen desorption from III-nitride microdisk resonator surfaces is shown to increase optical attenuation of whispering gallery modes by 100 cm-1 at λ = 450 nm. Comparison of photoinduced oxygen desorption in unintentionally and n+-doped microdisks suggests that the spectral changes originate from the unpinning of the surface Fermi level, likely taking place at etched nonpolar III-nitride sidewalls. An oxygen-rich surface prepared by thermal annealing results in a broadband Q improvement to state-of-the-art values exceeding 1 × 104 at 2.6 eV. Such findings emphasize the importance of optically active surface states and their passivation for future nanoscale III-nitride optoelectronic and photonic devices.

Measurement of the adsorption energy difference between ortho- and para-D2 on an amorphous ice surface.

PubMed

Amiaud, L; Momeni, A; Dulieu, F; Fillion, J H; Matar, E; Lemaire, J-L

2008-02-08

Molecular hydrogen interaction on water ice surfaces is a major process taking place in interstellar dense clouds. By coupling laser detection and classical thermal desorption spectroscopy, it is possible to study the effect of rotation of D(2) on adsorption on amorphous solid water ice surfaces. The desorption profiles of ortho- and para-D(2) are different. This difference is due to a shift in the adsorption energy distribution of the two lowest rotational states. Molecules in J''=1 rotational state are on average more strongly bound to the ice surface than those in J''=0 rotational state. This energy difference is estimated to be 1.4+/-0.3 meV. This value is in agreement with previous calculation and interpretation. The nonspherical wave function J'' =1 has an interaction with the asymmetric part of the adsorption potential and contributes positively in the binding energy.

Observation of the adsorption and desorption of vibrationally excited molecules on a metal surface

NASA Astrophysics Data System (ADS)

Shirhatti, Pranav R.; Rahinov, Igor; Golibrzuch, Kai; Werdecker, Jörn; Geweke, Jan; Altschäffel, Jan; Kumar, Sumit; Auerbach, Daniel J.; Bartels, Christof; Wodtke, Alec M.

2018-06-01

The most common mechanism of catalytic surface chemistry is that of Langmuir and Hinshelwood (LH). In the LH mechanism, reactants adsorb, become thermalized with the surface, and subsequently react. The measured vibrational (relaxation) lifetimes of molecules adsorbed at metal surfaces are in the range of a few picoseconds. As a consequence, vibrational promotion of LH chemistry is rarely observed, with the exception of LH reactions occurring via a molecular physisorbed intermediate. Here, we directly detect adsorption and subsequent desorption of vibrationally excited CO molecules from a Au(111) surface. Our results show that CO (v = 1) survives on a Au(111) surface for 1 × 10-10 s. Such long vibrational lifetimes for adsorbates on metal surfaces are unexpected and pose an interesting challenge to the current understanding of vibrational energy dissipation on metal surfaces. They also suggest that vibrational promotion of surface chemistry might be more common than is generally believed.

Kinetic Monte Carlo modeling of chemical reactions coupled with heat transfer.

PubMed

Castonguay, Thomas C; Wang, Feng

2008-03-28

In this paper, we describe two types of effective events for describing heat transfer in a kinetic Monte Carlo (KMC) simulation that may involve stochastic chemical reactions. Simulations employing these events are referred to as KMC-TBT and KMC-PHE. In KMC-TBT, heat transfer is modeled as the stochastic transfer of "thermal bits" between adjacent grid points. In KMC-PHE, heat transfer is modeled by integrating the Poisson heat equation for a short time. Either approach is capable of capturing the time dependent system behavior exactly. Both KMC-PHE and KMC-TBT are validated by simulating pure heat transfer in a rod and a square and modeling a heated desorption problem where exact numerical results are available. KMC-PHE is much faster than KMC-TBT and is used to study the endothermic desorption of a lattice gas. Interesting findings from this study are reported.

Quantifying atom addition reactions on amorphous solid water: a review of recent laboratory advances

NASA Astrophysics Data System (ADS)

He, Jiao; Vidali, Gianfranco

2018-06-01

Complex organic molecules found in space are mostly formed on and in the ice mantle covering interstellar dust grains. In clouds where ionizing irradiation is insignificant, chemical reactions on the ice mantle are dominated by thermal processes. Modeling of grain surface chemistry requires detailed information from the laboratory, including sticking coefficients, binding energies, diffusion energy barriers, mechanism of reaction, and chemical desorption rates. In this talk, recent laboratory advances in obtaining these information would be reviewed. Specifically, this talk will focus on the efforts in our group in: 1) Determining the mechanism of atomic hydrogen addition reactions on amorphous solid water (ASW); 2) Measuring the chemical desorption coefficient of H+O3-->O2+OH using the time-resolved scattering technique; and 3) Measuring the diffusion energy barrier of volatile molecules on ASW. Further laboratory studies will be suggested.This research was supported by NSF Astronomy & Astrophysics Research Grant #1615897.

Kinetic Monte Carlo modeling of chemical reactions coupled with heat transfer

NASA Astrophysics Data System (ADS)

Castonguay, Thomas C.; Wang, Feng

2008-03-01

In this paper, we describe two types of effective events for describing heat transfer in a kinetic Monte Carlo (KMC) simulation that may involve stochastic chemical reactions. Simulations employing these events are referred to as KMC-TBT and KMC-PHE. In KMC-TBT, heat transfer is modeled as the stochastic transfer of "thermal bits" between adjacent grid points. In KMC-PHE, heat transfer is modeled by integrating the Poisson heat equation for a short time. Either approach is capable of capturing the time dependent system behavior exactly. Both KMC-PHE and KMC-TBT are validated by simulating pure heat transfer in a rod and a square and modeling a heated desorption problem where exact numerical results are available. KMC-PHE is much faster than KMC-TBT and is used to study the endothermic desorption of a lattice gas. Interesting findings from this study are reported.

Diamond nanowires for highly sensitive matrix-free mass spectrometry analysis of small molecules.

PubMed

Coffinier, Yannick; Szunerits, Sabine; Drobecq, Hervé; Melnyk, Oleg; Boukherroub, Rabah

2012-01-07

This paper reports on the use of boron-doped diamond nanowires (BDD NWs) as an inorganic substrate for matrix-free laser desorption/ionization mass spectrometry (LDI-MS) analysis of small molecules. The diamond nanowires are prepared by reactive ion etching (RIE) with oxygen plasma of highly boron-doped (the boron level is 10(19) B cm(-3)) or undoped nanocrystalline diamond substrates. The resulting diamond nanowires are coated with a thin silicon oxide layer that confers a superhydrophilic character to the surface. To minimize droplet spreading, the nanowires were chemically functionalized with octadecyltrichlorosilane (OTS) and then UV/ozone treated to reach a final water contact angle of 120°. The sub-bandgap absorption under UV laser irradiation and the heat confinement inside the nanowires allowed desorption/ionization, most likely via a thermal mechanism, and mass spectrometry analysis of small molecules. A detection limit of 200 zeptomole for verapamil was demonstrated.

Development and Applications of Liquid Sample Desorption Electrospray Ionization Mass Spectrometry

NASA Astrophysics Data System (ADS)

Zheng, Qiuling; Chen, Hao

2016-06-01

Desorption electrospray ionization mass spectrometry (DESI-MS) is a recent advance in the field of analytical chemistry. This review surveys the development of liquid sample DESI-MS (LS-DESI-MS), a variant form of DESI-MS that focuses on fast analysis of liquid samples, and its novel analy-tical applications in bioanalysis, proteomics, and reaction kinetics. Due to the capability of directly ionizing liquid samples, liquid sample DESI (LS-DESI) has been successfully used to couple MS with various analytical techniques, such as microfluidics, microextraction, electrochemistry, and chromatography. This review also covers these hyphenated techniques. In addition, several closely related ionization methods, including transmission mode DESI, thermally assisted DESI, and continuous flow-extractive DESI, are briefly discussed. The capabilities of LS-DESI extend and/or complement the utilities of traditional DESI and electrospray ionization and will find extensive and valuable analytical application in the future.

On plate graphite supported sample processing for simultaneous lipid and protein identification by matrix assisted laser desorption ionization mass spectrometry.

PubMed

Calvano, Cosima Damiana; van der Werf, Inez Dorothé; Sabbatini, Luigia; Palmisano, Francesco

2015-05-01

The simultaneous identification of lipids and proteins by matrix assisted laser desorption ionization-mass spectrometry (MALDI-MS) after direct on-plate processing of micro-samples supported on colloidal graphite is demonstrated. Taking advantages of large surface area and thermal conductivity, graphite provided an ideal substrate for on-plate proteolysis and lipid extraction. Indeed proteins could be efficiently digested on-plate within 15 min, providing sequence coverages comparable to those obtained by conventional in-solution overnight digestion. Interestingly, detection of hydrophilic phosphorylated peptides could be easily achieved without any further enrichment step. Furthermore, lipids could be simultaneously extracted/identified without any additional treatment/processing step as demonstrated for model complex samples such as milk and egg. The present approach is simple, efficient, of large applicability and offers great promise for protein and lipid identification in very small samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Ammonia IRMS-TPD study on the distribution of acid sites in mordenite.

PubMed

Niwa, Miki; Suzuki, Katsuki; Katada, Naonobu; Kanougi, Tomonori; Atoguchi, Takashi

2005-10-13

Using an IRMS-TPD (temperature programmed desorption) of ammonia, we studied the nature, strength, crystallographic location, and distribution of acid sites of mordenite. In this method, infrared spectroscopy (IR) and mass spectroscopy (MS) work together to follow the thermal behavior of adsorbed and desorbed ammonia, respectively; therefore, adsorbed species were identified, and their thermal behavior was directly connected with the desorption of ammonia during an elevation of temperature. IR-measured TPD of the NH4(+) cation was similar to MS-measured TPD, thus showing the nature of Brønsted acidity. From the behavior of OH bands, it was found that the Brønsted acid sites consisted of two kinds of OH bands at high and low wavenumbers, ascribable to OH bands situated on 12- and 8-member rings (MR) of mordenite structure, respectively. The amount and strength of these Brønsted hydroxyls were measured quantitatively based on a theoretical equation using a curve fitting method. Up to ca. 30% of the exchange degree, NH4(+) was exchanged with Na+ on the 12-MR to arrive at saturation; therefore, in this region, the Brønsted acid site was situated on the large pore of 12-MR. The NH4(+) cation was then exchanged with Na+ on 8-MR, and finally exceeded the amount on 12-MR. In the 99% NH4-mordenite, Brønsted acid sites were located predominantly on the 8-MR more than on the 12-MR. Irrespective of the NH4(+) exchange degree, the strengths deltaH of Brønsted OH were 145 and 153 kJ mol(-1) on the 12- and 8-MR, respectively; that is, the strength of Brønsted acid site on the 8-MR was larger than that on the 12-MR. A density functional theory (DFT) calculation supported the difference in the strengths of the acid sites. Catalytic cracking activity of the Brønsted acid sites on the 8-MR declined rapidly, while that on the 12-MR was remarkably kept. The difference in strength and/or steric capacity may cause such a difference in the life of a catalyst.

Development of a miniaturized diffusive sampler for true breathing-zone sampling and thermal desorption gas chromatographic analysis.

PubMed

Lindahl, Roger; Levin, Jan-Olof; Sundgren, Margit

2009-07-01

Exposure measurements should be performed as close as possible to the nose and mouth for a more correct assessment of exposure. User-friendly sampling equipment, with a minimum of handling before, during and after measurement, should not affect ordinary work. In diffusive (passive) sampling, no extra equipment as sampling pumps is needed, making the measurements more acceptable to the user. The diffusive samplers are normally attached on a shoulder, on a breast-pocket or on the lapel. There are, however, difficulties if true breathing-zone sampling is to be performed, since available diffusive samplers normally cannot be arranged close to the nose/mouth. The purpose of this work was to study the performance of a miniaturized tube type diffusive sampler attached to a headset for true breathing-zone sampling. The basis for this miniaturization was the Perkin Elmer ATD tube. Both the size of the tube and the amount of adsorbent was decreased for the miniaturized sampler. A special tube holder to be used with a headset was designed for the mini tube. The mini tube is thermally desorbed inside a standard PE tube. The new sampler was evaluated for the determination of styrene, both in laboratory experiments and in field measurements. As reference method, diffusive sampling with standard Perkin Elmer tubes, thermal desorption and gas chromatographic (GC) analysis was used. The sampling rate was determined to 0.356 mL min(-1) (CV 9.6%) and was not significantly affected by concentration, sampling time or relative humidity.

Supercritical Fluid Extraction and Analysis of Tropospheric Aerosol Particles

NASA Astrophysics Data System (ADS)

Hansen, Kristen J.

An integrated sampling and supercritical fluid extraction (SFE) cell has been designed for whole-sample analysis of organic compounds on tropospheric aerosol particles. The low-volume extraction cell has been interfaced with a sampling manifold for aerosol particle collection in the field. After sample collection, the entire SFE cell was coupled to a gas chromatograph; after on-line extraction, the cryogenically -focused sample was separated and the volatile compounds detected with either a mass spectrometer or a flame ionization detector. A 20-minute extraction at 450 atm and 90 ^circC with pure supercritical CO _2 is sufficient for quantitative extraction of most volatile compounds in aerosol particle samples. A comparison between SFE and thermal desorption, the traditional whole-sample technique for analyses of this type, was performed using ambient aerosol particle samples, as well as samples containing known amounts of standard analytes. The results of these studies indicate that SFE of atmospheric aerosol particles provides quantitative measurement of several classes of organic compounds. SFE provides information that is complementary to that gained by the thermal desorption analysis. The results also indicate that SFE with CO _2 can be validated as an alternative to thermal desorption for quantitative recovery of several organic compounds. In 1989, the organic constituents of atmospheric aerosol particles collected at Niwot Ridge, Colorado, along with various physical and meteorological data, were measured during a collaborative field study. Temporal changes in the composition of samples collected during summertime at the rural site were studied. Thermal desorption-GC/FID was used to quantify selected compounds in samples collected during the field study. The statistical analysis of the 1989 Niwot Ridge data set is presented in this work. Principal component analysis was performed on thirty-one variables selected from the data set in order to ascertain different source and process components, and to examine concentration changes in groups of variables with respect to time of day and meteorological conditions. Seven orthogonal groups of variables resulted from the statistical analysis; the groups serve as molecular markers for different biologic and anthropogenic emission sources. In addition, the results of the statistical analysis were used to investigate how several emission source contributions vary with respect to local atmospheric dynamics. Field studies were conducted in the urban environment in and around Boulder, CO. to characterize the dynamics, chemistry, and emission sources which affect the composition and concentration of different size-fractions of aerosol particles in the Boulder air mass. Relationships between different size fractions of particles and some gas-phase pollutants were elucidated. These field studies included an investigation of seasonal variations in the organic content and concentration of aerosol particles, and how these characteristics are related to local meteorology and to the concentration of some gas-phase pollutants. The elemental and organic composition of aerosol particles was investigated according to particle size in preliminary studies of size-differentiated samples of aerosol particles. In order to aid in future studies of urban aerosol particles, samples were collected at a forest fire near Boulder. Molecular markers specific to wood burning processes will be useful indicators of residential wood burning activities in future field studies.

Kinetic and geometric isotope effects originating from different adsorption potential energy surfaces: cyclohexane on Rh(111).

PubMed

Koitaya, Takanori; Shimizu, Sumera; Mukai, Kozo; Yoshimoto, Shinya; Yoshinobu, Jun

2012-06-07

Novel isotope effects were observed in desorption kinetics and adsorption geometry of cyclohexane on Rh(111) by the use of infrared reflection absorption spectroscopy, temperature programmed desorption, photoelectron spectroscopy, and spot-profile-analysis low energy electron diffraction. The desorption energy of deuterated cyclohexane (C(6)D(12)) is lower than that of C(6)H(12). In addition, the work function change by adsorbed C(6)D(12) is smaller than that by adsorbed C(6)H(12). These results indicate that C(6)D(12) has a shallower adsorption potential than C(6)H(12) (vertical geometric isotope effect). The lateral geometric isotope effect was also observed in the two-dimensional cyclohexane superstructures as a result of the different repulsive interaction between interfacial dipoles. The observed isotope effects should be ascribed to the quantum nature of hydrogen involved in the C-H···metal interaction.

Study of the Decomposition and Phase Transition of Uranium Nitride under UHV Conditions via TDS, XRD, SEM, and XPS.

PubMed

Wang, Xiaofang; Long, Zhong; Bin, Ren; Yang, Ruilong; Pan, Qifa; Li, Fangfang; Luo, Lizhu; Hu, Yin; Liu, Kezhao

2016-11-07

Uranium nitrides are among the most promising fuels for Generation IV nuclear reactors, but until now, very little has been known about their thermal stability properties under nonequilibrium conditions. In this work, thermal decomposition of nitrogen-rich uranium nitride (denoted as UN 2-x ) under ultrahigh-vacuum (UHV) conditions was investigated by thermal desorption spectroscopy (TDS). It has been shown that the nitrogen TDS spectrum consists of two peaks at about 723 and 1038 K. The X-ray diffraction, scanning electron microscopy, and X-ray photoelectron microscopy results indicate that UN 2-x (UN 2 phase) decomposed into the α-U 2 N 3 phase in the first step and the α-U 2 N 3 phase decomposed into the UN phase in the second step.

Hierarchically porous LaFeO3 perovskite prepared from the pomelo peel bio-template for catalytic oxidation of NO

NASA Astrophysics Data System (ADS)

Zhao, Shaojun; Wang, Li; Wang, Ying; Li, Xing

2018-05-01

In this paper, pomelo peel was used as biological template to obtain hierarchically porous LaFeO3 perovskite for the catalytic oxidation of NO to NO2. In addition, X-ray diffraction (XRD), scanning electron microscopy (SEM), N2 adsorption-desorption analyses, X-ray photoelectron spectra (XPS), NO temperature-programmed desorption (NO-TPD), oxygen temperature-programmed desorption (O2-TPD) and hydrogen temperature-programmed reduction (H2-TPR) were used to investigate the micro-structure and the redox properties of the hierarchically porous LaFeO3 perovskite prepared from pomelo peel biological template and the LaFeO3 perovskite without the biological template. The results indicated that the hierarchically porous LaFeO3 perovskite successfully replicated the porous structure of pomelo peel with high specific surface area. Compared to the LaFeO3 perovskite prepared without the pomelo peel template, the hierarchically porous LaFeO3 perovskite showed better catalytic oxidization of NO to NO2 under the same conditions. The maximum NO conversions for LaFeO3 prepared with and without template were 90% at 305 °C and 76% at 313 °C, respectively. This is mainly attributed to the higher ratio of Fe4+/Fe3+, the hierarchically porous structure with more adsorbed oxygen species and higher surface area for the hierarchically porous LaFeO3 perovskite compared with the sample prepared without the pomelo peel template.

Evaluation of an adsorption system to concentrate VOC in air streams prior to catalytic incineration.

PubMed

Campesi, María A; Luzi, Carlos D; Barreto, Guillermo F; Martínez, Osvaldo M

2015-05-01

Catalytic combustion is a well-developed process for the removal of volatile organic compounds (VOCs). In order to reduce both the amount of catalyst needed for incineration and the surface area of recuperative heat exchangers, an evaluation of the use of thermal swing adsorption as a previous step for VOC concentration is made. An air stream containing ethyl acetate and ethanol (employed as solvents in printing processes) has been taken as a case study. Based on the characteristics of the adsorption/desorption system and the properties of the stream to be treated, a monolithic rotor concentrator with activated carbon as adsorbent material is adopted. Once the temperature of the inlet desorption stream TD is chosen, the minimum possible desorption flow rate, WD,min, and the amount of adsorbent material can be properly defined according to the extent of the Mass Transfer Zone (MTZ) at the end of the adsorption stage. An approximate procedure to speed up the calculations needed for sizing the bed and predicting the operating variables is also presented. In the case studied here, the concentration of the VOC stream can reach 6 times that of the primary effluent when TD = 200 °C is chosen. Copyright © 2015 Elsevier Ltd. All rights reserved.

Reactive Desorption and Radiative Association as Possible Drivers of Complex Molecule Formation in the Cold Interstellar Medium

NASA Astrophysics Data System (ADS)

Vasyunin, A. I.; Herbst, Eric

2013-05-01

The recent discovery of terrestrial-type organic species such as methyl formate and dimethyl ether in the cold interstellar gas has proved that the formation of organic matter in the Galaxy begins at a much earlier stage of star formation than was previously thought. This discovery represents a challenge for astrochemical modelers. The abundances of these molecules cannot be explained by the previously developed "warm-up" scenario, in which organic molecules are formed via diffusive chemistry on surfaces of interstellar grains starting at 30 K, and then released to the gas at higher temperatures during later stages of star formation. In this article, we investigate an alternative scenario in which complex organic species are formed via a sequence of gas-phase reactions between precursor species formed on grain surfaces and then ejected into the gas via efficient reactive desorption, a process in which non-thermal desorption occurs as a result of conversion of the exothermicity of chemical reactions into the ejection of products from the surface. The proposed scenario leads to reasonable if somewhat mixed results at temperatures as low as 10 K and may be considered as a step toward the explanation of abundances of terrestrial-like organic species observed during the earliest stages of star formation.

Energy transfer and photochemistry on a metal surface: Mo(CO)/sub 6/ on Rh(100)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Germer, T.A.; Ho, W.

1989-05-01

The occurrence of photoinduced reactions on solid surfaces depends on the relative rates between the excited-state decomposition and the energy transfer to the surface. In this study, the photodecomposition of Mo(CO)/sub 6/ on Rh(100) at 90 K by 325-nm UV irradiation has been studied as a function of coverage and surface preparation using thermal desorption spectroscopy, electron energy-loss spectroscopy, and photoinduced desorption spectroscopy. It is found that Mo(CO)/sub 6/ adsorbs dissociatively on Rh(100) into carbonyl fragments and CO in the first monolayer and molecularly in multilayers. Photoinduced desorption of CO is observed for the multilayers adsorbed onto the dissociated firstmore » layer via a nonthermal electronic excitation of adsorbed metal carbonyls. The presence of the metal surface prevents complete decarbonylation as in the gas phase; deexcitation of electronically excited carbonyls is not sufficiently fast to quench all the observed photochemistry. It is also found that Mo(CO)/sub 6/ adsorbs molecularly on a presaturated CO ordered overlayer on Rh(100) and undergoes photodissociation to a greater degree than on the dissociated and disordered surface of carbonyl fragments. The ordered CO layer effectively screens the interaction between the molecular carbonyls and the Rh(100) layer surface.« less

Initial Steps of Rubicene Film Growth on Silicon Dioxide.

PubMed

Scherwitzl, Boris; Lukesch, Walter; Hirzer, Andreas; Albering, Jörg; Leising, Günther; Resel, Roland; Winkler, Adolf

2013-02-28

The film growth of the conjugated organic molecule rubicene on silicon dioxide was studied in detail. Since no structural data of the condensed material were available, we first produced high quality single crystals from solution and determined the crystal structure. This high purity material was used to prepare ultrathin films under ultrahigh vacuum conditions, by physical vapor deposition. Thermal desorption spectroscopy (TDS) was applied to delineate the adsorption and desorption kinetics. It could be shown that the initial sticking coefficient is only 0.2 ± 0.05, but the sticking coefficient increases with increasing coverage. TDS further revealed that first a closed, weakly bound bilayer develops (wetting layer), which dewets after further deposition of rubicene, leading to an island-like layer. These islands are crystalline and exhibit the same structure as the solution grown crystals. The orientation of the crystallites is with the (001) plane parallel to the substrate. A dewetting of the closed bilayer was also observed when the film was exposed to air. Furthermore, Ostwald ripening of the island-like film takes place under ambient conditions, leading to films composed of few, large crystallites. From TDS, we determined the heat of evaporation from the multilayer islands to be 1.47 eV, whereas the desorption energy from the first layer is only 1.25 eV.

Initial Steps of Rubicene Film Growth on Silicon Dioxide

PubMed Central

2013-01-01

The film growth of the conjugated organic molecule rubicene on silicon dioxide was studied in detail. Since no structural data of the condensed material were available, we first produced high quality single crystals from solution and determined the crystal structure. This high purity material was used to prepare ultrathin films under ultrahigh vacuum conditions, by physical vapor deposition. Thermal desorption spectroscopy (TDS) was applied to delineate the adsorption and desorption kinetics. It could be shown that the initial sticking coefficient is only 0.2 ± 0.05, but the sticking coefficient increases with increasing coverage. TDS further revealed that first a closed, weakly bound bilayer develops (wetting layer), which dewets after further deposition of rubicene, leading to an island-like layer. These islands are crystalline and exhibit the same structure as the solution grown crystals. The orientation of the crystallites is with the (001) plane parallel to the substrate. A dewetting of the closed bilayer was also observed when the film was exposed to air. Furthermore, Ostwald ripening of the island-like film takes place under ambient conditions, leading to films composed of few, large crystallites. From TDS, we determined the heat of evaporation from the multilayer islands to be 1.47 eV, whereas the desorption energy from the first layer is only 1.25 eV. PMID:23476720

Evaluation of solid-phase microextraction desorption parameters for fast GC analysis of cocaine in coca leaves.

PubMed

Ilias, Yara; Bieri, Stefan; Christen, Philippe; Veuthey, Jean-Luc

2006-08-01

By its simplicity and rapidity, solid-phase microextraction (SPME) appears as an interesting alternative for sample introduction in fast gas chromatography (fast GC). This combination depends on numerous parameters affecting the desorption step (i.e., the release of compounds from the SPME fiber coating to the GC column). In this study, different liner diameters, injection temperatures, and gas flow rates are evaluated to accelerate the thermal desorption process in the injection port. This process is followed with real-time direct coupling a split/splitless injector to a mass spectrometer by means of a short capillary. It is shown that an effective, quantitative, and rapid transfer of cocaine (COC) and cocaethylene (CE) is performed with a 0.75-mm i.d. liner, at 280 degrees C and 4 mL/min gas flow rate. The 7-microm polydimethylsiloxane (PDMS) coating is selected for combination with fast GC because the 100-microm PDMS fiber presents some limitations caused by fiber bleeding. Finally, the developed SPME-fast GC method is applied to perform in less than 5 min, the quantitation of COC extracted from coca leaves by focused microwave-assisted extraction. An amount of 7.6 +/- 0.5 mg of COC per gram of dry mass is found, which is in good agreement with previously published results.

Distribution law of temperature changes during methane adsorption and desorption in coal using infrared thermography technology

NASA Astrophysics Data System (ADS)

Zhao, Dong; Chen, Hao; An, Jiangfei; Zhou, Dong; Feng, Zengchao

2018-05-01

Gas adsorption and desorption is a thermodynamic process that takes place within coal as temperature changes and that is related to methane (CH4) storage. As infrared thermographic technology has been applied in this context to measure surface temperature changes, the aim of this research was to further elucidate the distribution law underlying this process as well as the thermal effects induced by heat adsorption and desorption in coal. Specimens of two different coal ranks were used in this study, and the surface temperature changes seen in the latter were detected. A contour line map was then drawn on the basis of initial results enabling a distribution law of temperature changes for samples. The results show that different regions of coal sample surfaces exhibit different heating rates during the adsorption process, but they all depends on gas storage capacity to a certain extent. It proposes a correlation coefficient that expresses the relationship between temperature change and gas adsorption capacity that could also be used to evaluate the feasibility of coalbed CH4 extraction in the field. And finally, this study is deduced a method to reveal the actual adsorption capacity of coal or CH4 reservoirs in in situ coal seams.

Development of a Thermal Desorption Gas Chromatography-Mass Spectrometry Analysis Method for Airborne Dichlorodiphenyltrichloroethane

DTIC Science & Technology

2013-05-28

span of 1-250 ng DDT. Furthermore, laboratory and field experiments utilizing this method confirmed that significant DDT concentration differences ... different between the two sample introduction methods when comparing the same DDT mass which may be due to differences in the precision of split...degradation of DDT was significantly different between the liquid and TD methods (t-test; p < 0.001). For TD analyses the relative percent

Nonlinear Effects in High Electric Fields

DTIC Science & Technology

1993-04-06

ion microscope above protruding atoms. Experiments to verify our theoret- ical predictions have been performed at the Fritz - Haber -Institute, see...Block’s experimental group at the Fritz - Haber -Institut in Berlin. A recent topic was thermal field desorption of hydrogen for which we have been able...Suchorskil, W. A. Schmidt’, J. H. Block’ and H. J. Kreuzer2 To be published in Surface Science ’Fitz- Haber Institut der Max-Planck-Gesellschaft

Thermal Desorption Capability Development for Enhanced On-site Health Risk Assessment: HAPSITE (registered trademark) ER Passive Sampling in the Field

DTIC Science & Technology

2015-06-07

Field-Portable Gas Chromatograph-Mass Spectrometer.” Forensic Toxicol, 2006, 24, 17-22. Smith, P. “Person-Portable Gas Chromatography : Rapid Temperature...bench-top Gas Chromatograph-Mass Spectrometer (GC-MS) system (ISQ). Nine sites were sampled and analyzed for compounds using Environmental Protection...extraction methods for Liquid Chromatography -MS (LC- MS). Additionally, TD is approximately 1000X more sensitive, requires minimal sample preparation

Thermal-desorption measurements for estimating bakeout characteristics of vacuum devices

NASA Astrophysics Data System (ADS)

Beavis, L.

1981-11-01

This discussion will be confined to outgassing phenomena; although gettering (sinks) or permeation (transfer through the entire vacuum wall) are imported in long term prediction. Measuring outgassing rates directly is complicated by the dynamic interaction between the samples being measured and the apparatus in which the measurements are made. Thermoesorption data are presented for molybdenum, nickel, Fe-Ni-Co alloy, copper, Cu-Be alloy, molybdenum sealing glass ceramic, and high-alumina ceramic.

Thermo-analytical and physico-chemical characterisation of organoclays and polymer-clay nacomposites

NASA Astrophysics Data System (ADS)

Cunningham, Andrew

A variety of modified clay minerals have been screened to determine their effectiveness as agents for the production of polystyrene-clay nanocomposites. The n-alkylammonium and n-alkyltrimethylammonium surfactants employed to compatibilise the aluminosilicate layers of the minerals were shown to degrade through a series of stages and mechanisms to yield a hydrocarbon product mixture consisting of a homologous series of saturated and unsaturated hydrocarbons, also, the dehydrocyclisation (DHC) of fragmented alkyl chains was shown to lead to the production of various ring compounds which included substituted cycloalkenes, benzene and toluene.The thermal stability of various cation exchanged modification treatments have been analysed. These organoclays have been characterised by XRD, TGA and TG-MS. The evolved gas analysis conducted by TG-MS was employed to identify which products were being thermally desorbed under thermal events previously seen when using TGA. In particular attention was paid to the activity of these materials with respect to the formation of linear, branched and cyclic aliphatics and aromatics from the feedstock surfactants.Intra-series comparisons of different organoclays showed that as the alkyl chain length of the n-alkylammonium surfactants was increased the concentration of thermal desorption products at approximately 400 °C was also increased. However, characterisation of n-alkyltrimethylammonium exchanged MMT showed that the concentration of thermal desorption products at lower temperatures (approximately 250 °C) increased with alkyl chain length between C[n] = 8 - 16. TG-MS analysis showed that this was mostly due to the DHC of alkyl fragments. These compounds appear to have been largely overlooked in related literature.SWa-1, a clay containing greater concentrations of structural iron, showed higher T[max] values for n-alkylammonium surfactant thermal desorption than similarly exchanged SAz-1. This may be evidence of a current theory that structural iron acts as a radical trap. This is thought to significantly reduce the catalytic activity of the clay's acid sites until higher temperatures. The formulation of polystyrene-clay nanocomposites (PSCNs) by in-situ polymerisation led to various results pertaining to their thermal stability. The relative effectiveness of various initiator species for the production of the most thermally stable PSCNs was AIBN > BPO > SPS > APS > AIBA. Lower radical initiator and organic modifier concentrations led to the production of PSCNs with higher thermal stability. The relative effectiveness of these various organoclays for the production of more thermally stable PSCNs was MCBP-Cn > C15A > C20A " C10A. The preparation method was shown to be effective for producing exfoliated nanocomposites for up to 1 wt% of the various organoclays using AIBN and BPO as initiators. The MCBP-Cn PSCNs remained exfoliated up to 5 wt% , they also showed higher thermal stability when compared with the commercial products, which XRD results showed to remain stacked at organoclay loadings > 1 wt%.A novel one-pot synthesis method for the production of PSCN, by the in-situ polymerisation of PS in the presence of decanamide (an uncharged surfactant) and Na-MMT, was shown to be successful. Whereas, other novel PSCN formulations incorporating N-vinylformamide and the amphoteric surfactant foamtaine SCAB were shown to be encouraging but have, so far, had limited success.In contrast, the analysis of industrially produced unsaturated polyester-clay nanocomposites showed very little increase in the thermal stability of the material. Associated analyses indicated increased dimensional stability of the material, AFM analysis showed that imaging of the clay dispersal was possible by this macroscopic technique. Also, ATR-FTIR analysis of the UPR and UPCN, showed that although not exfoliated the silane modified-MMT had a good synergistic effect on the overall material by reducing the formation of combustion products.The thermal stability and associated studies of kaolin-phenylphosphonic acid (KPPA) complexes was also conducted. PPA was shown to intercalate the kaolin crystal structure forming an expanded phase that exhibited remarkable thermal stability (Tmax = 660 °C). 31P MAS NMR of all the KPPA samples showed three peaks (at +1.2, -3.7 and -7.3 ppm) which represented PPA existing in three non-equivalent bonding states at the kaolin surface. The high thermal stability of these hybrid materials was evident from these studies. This research into the use of covalently bound intercalates in nanocomposite manufacture signifies the necessity for further research.

Analysis of trace contamination of phthalate esters in ultrapure water using a modified solid-phase extraction procedure and automated thermal desorption-gas chromatography/mass spectrometry.

PubMed

Liu, Hsu-Chuan; Den, Walter; Chan, Shu-Fei; Kin, Kuan Tzu

2008-04-25

The present study was aimed to develop a procedure modified from the conventional solid-phase extraction (SPE) method for the analysis of trace concentration of phthalate esters in industrial ultrapure water (UPW). The proposed procedure allows UPW sample to be drawn through a sampling tube containing hydrophobic sorbent (Tenax TA) to concentrate the aqueous phthalate esters. The solid trap was then demoisturized by two-stage gas drying before subjecting to thermal desorption and analysis by gas chromatography-mass spectrometry. This process removes the solvent extraction procedure necessary for the conventional SPE method, and permits automation of the analytical procedure for high-volume analyses. Several important parameters, including desorption temperature and duration, packing quantity and demoisturizing procedure, were optimized in this study based on the analytical sensitivity for a standard mixture containing five different phthalate esters. The method detection limits for the five phthalate esters were between 36 ng l(-1) and 95 ng l(-1) and recovery rates between 15% and 101%. Dioctyl phthalate (DOP) was not recovered adequately because the compound was both poorly adsorbed and desorbed on and off Tenax TA sorbents. Furthermore, analyses of material leaching from poly(vinyl chloride) (PVC) tubes as well as the actual water samples showed that di-n-butyl phthalate (DBP) and di(2-ethylhexyl) phthalate (DEHP) were the common contaminants detected from PVC contaminated UPW and the actual UPW, as well as in tap water. The reduction of DEHP in the production processes of actual UPW was clearly observed, however a DEHP concentration of 0.20 microg l(-1) at the point of use was still being quantified, suggesting that the contamination of phthalate esters could present a barrier to the future cleanliness requirement of UPW. The work demonstrated that the proposed modified SPE procedure provided an effective method for rapid analysis and contamination identification in UPW production lines.

Novel Montmorillonite/TiO₂/MnAl-Mixed Oxide Composites Prepared from Inverse Microemulsions as Combustion Catalysts.

PubMed

Napruszewska, Bogna D; Michalik-Zym, Alicja; Rogowska, Melania; Bielańska, Elżbieta; Rojek, Wojciech; Gaweł, Adam; Wójcik-Bania, Monika; Bahranowski, Krzysztof; Serwicka, Ewa M

2017-11-19

A novel design of combustion catalysts is proposed, in which clay/TiO₂/MnAl-mixed oxide composites are formed by intermixing exfoliated organo-montmorillonite with oxide precursors (hydrotalcite-like in the case of Mn-Al oxide) obtained by an inverse microemulsion method. In order to assess the catalysts' thermal stability, two calcination temperatures were employed: 450 and 600 °C. The composites were characterized with XRF (X-ray fluorescence), XRD (X-ray diffraction), HR SEM (high resolution scanning electron microscopy, N₂ adsorption/desorption at -196 °C, and H₂ TPR (temperature programmed reduction). Profound differences in structural, textural and redox properties of the materials were observed, depending on the presence of the TiO₂ component, the type of neutralization agent used in the titania nanoparticles preparation (NaOH or NH₃ (aq)), and the temperature of calcination. Catalytic tests of toluene combustion revealed that the clay/TiO₂/MnAl-mixed oxide composites prepared with the use of ammonia showed excellent activity, the composites obtained from MnAl hydrotalcite nanoparticles trapped between the organoclay layers were less active, but displayed spectacular thermal stability, while the clay/TiO₂/MnAl-mixed oxide materials obtained with the aid of NaOH were least active. The observed patterns of catalytic activity bear a direct relation to the materials' composition and their structural, textural, and redox properties.

Technical Requirements for On-Site Thermal Desorption of Solid Media Contaminated with Hazardous Chlorinated Organics

DTIC Science & Technology

1997-09-18

scrubbers , detectable dioxin/furans may occur, since dioxin/furans are much more soluble in organics than in water. Carbon adsorption is frequently...air pollution control device is required. Acid gases may be controlled by using a wet or dry scrubber or by using a coated baghouse. Operating...unit: 1. exit treated waste temperature; 2. baghouse pressure drop, venturi pressure drop, or drop in liquid/gas ratio; 3. waste feed rate; 4

Modeling of thin-film GaAs growth

NASA Technical Reports Server (NTRS)

Heinbockel, J. H.

1981-01-01

A solid Monte Carlo model is constructed for the simulation of crystal growth. The model assumes thermally accommodated adatoms impinge upon the surface during a delta time interval. The surface adatoms are assigned a random energy from a Boltzmann distribution, and this energy determines whether the adatoms evaporate, migrate, or remain stationary during the delta time interval. For each addition or migration of an adatom, potential wells are adjusted to reflect the absorption, migration, or desorption potential changes.

Sputtering of sodium on the planet Mercury

NASA Technical Reports Server (NTRS)

Mcgrath, M. A.; Johnson, R. E.; Lanzerotti, L. J.

1986-01-01

It is shown here that ion sputtering cannot account for the observed neutral sodium vapor column density on Mercury, but that it is an important loss mechanism for Na. Photons are likely to be the dominant stimulus, both directly through photodesorption and indirectly through thermal desorption of absorbed Na. It is concluded that the atmosphere produced is characterized by the planet's surface temperature, with the ion-sputtered Na contributing to a lesser, but more extended, component of the atmosphere.

The evolution of helium from aged Zr tritides: A thermal helium desorption spectrometry study

NASA Astrophysics Data System (ADS)

Cheng, G. J.; Huang, G.; Chen, M.; Zhou, X. S.; Liu, J. H.; Peng, S. M.; Ding, W.; Wang, H. F.; Shi, L. Q.

2018-02-01

The evolution of He from Zr-tritides was investigated for aging times up to about 6.5 years using analytical thermal helium desorption spectrometry (THDS). Zr films were deposited onto Mo substrates and then converted into Zr-tritides (ZrT1.70∼1.95) inside a tritiding apparatus loaded with pure tritium gas. During aging, there are at least five forms of He in Zr-tritides, and more than 99% of He atoms are in the form of He bubbles. The isolated He bubbles in lattices begin to link with each other when the He/Zr atom ratio reaches about 0.21, and are connected to grain boundaries or dislocation networks at He concentration of He/Zr ≈ 0.26. An interconnected system of channels decorated by bubbles evolves from the network dislocations, dislocation loops and internal boundaries. These He filled networks are formed completely when the He/Zr atom ratio is about 0.38. Once the He/Zr reached about 0.45, the networks of He bubble penetrate to the film surface and He begins an "accelerated release". This critical ratio of He to Zr for He accelerated release is much greater than that found previously for Ti-tritides (0.23-0.30). The difference of He retention in Zr-tritides and Ti-tritides was also discussed in this paper.

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

NASA Astrophysics Data System (ADS)

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

2017-10-01

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

Reactivity of O2 on Pd/Ru(0001) and PdRu/Ru(0001) surface alloys

NASA Astrophysics Data System (ADS)

Farías, D.; Minniti, M.; Miranda, R.

2017-05-01

The reactivity of a Pd monolayer epitaxially grown on Ru(0001) toward O2 has been investigated by molecular beam techniques. O2 initial sticking coefficients were determined using the King and Wells method in the incident energy range of 40-450 meV and for sample temperatures of 100 K and 300 K, and compared to the corresponding values measured on the clean Ru(0001) and Pd(111) surfaces. In contrast to the high reactivity shown by Ru(0001) at 100 K, the Pd/Ru(0001) system exhibits a monotonic decrease in the sticking probability of O2 as a function of normal incident energy. At room temperature, the system was found to be inert. Thermal desorption measurements show that O2 is adsorbed molecularly at 100 K. A completely different behaviour has been measured for the Pd0.95Ru0.05/Ru(0001) surface alloy. On this surface, the O2 sticking probability increases with incident energy and resembles the one observed on the clean Ru(0001) surface, even at 300 K. Thermal desorption measurements point to dissociative adsorption of O2 in this system. Both the charge transfer from the Pd to the Ru substrate and the compressive strain on the Pd monolayer contribute to decrease in the reactivity of the Pd/Ru(0001) system well below those of both Ru(0001) and Pd(111).

Enhanced CO2 adsorptive performance of PEI/SBA-15 adsorbent using phosphate ester based surfactants as additives.

PubMed

Cheng, Dandan; Liu, Yue; Wang, Haiqiang; Weng, Xiaole; Wu, Zhongbiao

2015-12-01

In this study, a series of polyetherimide/SBA-15: 2-D hexagonal P6mm, Santa Barbara USA (PEI/SBA-15) adsorbents modified by phosphoric ester based surfactants (including tri(2-ethylhexyl) phosphate (TEP), bis(2-ethylhexyl) phosphate (BEP) and trimethyl phosphonoacetate (TMPA)) were prepared for CO2 adsorption. Experimental results indicated that the addition of TEP and BEP had positive effects on CO2 adsorption capacity over PEI/SBA-15. In particular, the CO2 adsorption amount could be improved by around 20% for 45PEI-5TEP/SBA-15 compared to the additive-free adsorbent. This could be attributed to the decrease of CO2 diffusion resistance in the PEI bulk network due to the interactions between TEP and loaded PEI molecules, which was further confirmed by adsorption kinetics results. In addition, it was also found that the cyclic performance of the TEP-modified adsorbent was better than the surfactant-free one. This could be due to two main reasons, based on the results of in situ DRIFT and TG-DSC tests. First and more importantly, adsorbed CO2 species could be desorbed more rapidly over TEP-modified adsorbent during the thermal desorption process. Furthermore, the enhanced thermal stability after TEP addition ensured lower degradation of amine groups during adsorption/desorption cycles. Copyright © 2015. Published by Elsevier B.V.

Water-Stable Metal-Organic Framework with Three Hydrogen-Bond Acceptors: Versatile Theoretical and Experimental Insights into Adsorption Ability and Thermo-Hydrolytic Stability.

PubMed

Roztocki, Kornel; Lupa, Magdalena; Sławek, Andrzej; Makowski, Wacław; Senkovska, Irena; Kaskel, Stefan; Matoga, Dariusz

2018-03-19

A new microporous cadmium metal-organic framework was synthesized both mechanochemically and in solution by using a sulfonyl-functionalized dicarboxylate linker and an acylhydrazone colinker. The three-dimensional framework is highly stable upon heating to 300 °C as well as in aqueous solutions at elevated temperatures or acidic conditions. The thermally activated material exhibits steep water vapor uptake at low relative pressures at 298 K and excellent recyclability up to 260 °C as confirmed by both quasi-equilibrated temperature-programmed desorption and adsorption (QE-TPDA) method as well as adsorption isotherm measurements. Reversible isotherms and hysteretic isobars recorded for the desorption-adsorption cycles indicate the maximum uptake of 0.19 g/g (at 298 K, up to p/p 0 = 1) or 0.18 g/g (at 1 bar, within 295-375 K range), respectively. The experimental isosteric heat of adsorption (48.9 kJ/mol) indicates noncoordinative interactions of water molecules with the framework. Exchange of the solvent molecules in the as-made material with water, performed in the single-crystal to single-crystal manner, allows direct comparison of both X-ray crystal structures. The single-crystal X-ray diffraction for the water-loaded framework demonstrates the orientation of water clusters in the framework cavities and reveals their strong hydrogen bonding with sulfonyl, acyl, and carboxylate groups of the two linkers. The grand canonical Monte Carlo (GCMC) simulations of H 2 O adsorption corroborate the experimental findings and reveal preferable locations of guest molecules in the framework voids at various pressures. Additionally, both experimental and GCMC simulation insights into the adsorption of CO 2 (at 195 K) on the activated framework are presented.

Selective enhancement of carbohydrate ion abundances by diamond nanoparticles for mass spectrometric analysis.

PubMed

Wu, Chieh-Lin; Wang, Chia-Chen; Lai, Yin-Hung; Lee, Hsun; Lin, Jia-Der; Lee, Yuan Tseh; Wang, Yi-Sheng

2013-04-16

Diamond nanoparticles (DNPs) were incorporated into matrix-assisted laser desorption/ionization (MALDI) samples to enhance the sensitivity of the mass spectrometer to carbohydrates. The DNPs optimize the MALDI sample morphology and thermalize the samples for thermally labile compounds because they have a high thermal conductivity, a low extinction coefficient in UV-vis spectral range, and stable chemical properties. The best enhancement effect was achieved when matrix, DNP, and carbohydrate solutions were deposited and vacuum-dried consecutively to form a trilayer sample morphology. It allows the direct identification of underivatized carbohydrates mixed with equal amount of proteins because no increase in the ion abundance of proteins was achieved. For dextran with an average molecular weight of 1500, the trilayer method typically improves the sensitivity by 79- and 7-fold in comparison to the conventional dried-droplet and thin-layer methods, respectively.

Apparatus for measurements of thermal and optical stimulated exo-electron emission and luminescence

NASA Astrophysics Data System (ADS)

Pokorný, P.; Novotný, M.; Fitl, P.; Zuklín, J.; Vlček, J.; Nikl, J.; Marešová, E.; Hruška, P.; Bulíř, J.; Drahokoupil, J.; Čerňanský, M.; Lančok, J.

2018-06-01

The purpose of the design, construction and implementation of vacuum apparatus for measuring simultaneously three or more stimulated phenomena in dielectrics and eventually semiconductors is to investigate those phenomena as a function of temperature and wavelength. The test of equipment and its functionality were carried out step by step (apparatus, components and control sample) and associated with the calculation of the main physical parameters. The tests of individual parts of the apparatus clearly confirmed that the design, construction and selected components fulfil or even exceed the required properties. On the basis of the measurement of selected sample, it was shown that even weak signals from the material can be detected from both thermally stimulated luminescence and thermally stimulated exo-electron emission moreover transmission and desorption can be measured. NaCl:Ni (0.2%) was chosen as the test material. The activation energies and frequency factor were calculated using the methods of different authors.

Upgrading non-oxidized carbon nanotubes by thermally decomposed hydrazine

NASA Astrophysics Data System (ADS)

Wang, Pen-Cheng; Liao, Yu-Chun; Liu, Li-Hung; Lai, Yu-Ling; Lin, Ying-Chang; Hsu, Yao-Jane

2014-06-01

We found that the electrical properties of conductive thin films based on non-oxidized carbon nanotubes (CNTs) could be further improved when the CNTs consecutively underwent a mild hydrazine adsorption treatment and then a sufficiently effective thermal desorption treatment. We also found that, after several rounds of vapor-phase hydrazine treatments and baking treatments were applied to an inferior single-CNT field-effect transistor device, the device showed improvement in Ion/Ioff ratio and reduction in the extent of gate-sweeping hysteresis. Our experimental results indicate that, even though hydrazine is a well-known reducing agent, the characteristics of our hydrazine-exposed CNT samples subject to certain treatment conditions could become more graphenic than graphanic, suggesting that the improvement in the electrical and electronic properties of CNT samples could be related to the transient bonding and chemical scavenging of thermally decomposed hydrazine on the surface of CNTs.

Synthesis and structure characterization of chromium oxide prepared by solid thermal decomposition reaction.

PubMed

Li, Li; Yan, Zi F; Lu, Gao Q; Zhu, Zhong H

2006-01-12

Mesoporous chromium oxide (Cr2O3) nanocrystals were first synthesized by the thermal decomposition reaction of Cr(NO3)3.9H2O using citric acid monohydrate (CA) as the mesoporous template agent. The texture and chemistry of chromium oxide nanocrystals were characterized by N2 adsorption-desorption isotherms, FTIR, X-ray diffraction (XRD), UV-vis, and thermoanalytical methods. It was shown that the hydrate water and CA are the crucial factors in influencing the formation of mesoporous Cr2O3 nanocrystals in the mixture system. The decomposition of CA results in the formation of a mesoporous structure with wormlike pores. The hydrate water of the mixture provides surface hydroxyls that act as binders, making the nanocrystals aggregate. The pore structures and phases of chromium oxide are affected by the ratio of precursor-to-CA, thermal temperature, and time.

Electrical properties of lanthanum chromite based ceramics in hydrogen and oxidizing atmospheres at high temperatures

NASA Astrophysics Data System (ADS)

Schmidt, V. H.

1981-06-01

Several results regarding the effect of hydrogen on lanthanum chromite were determined. Thermally-activated diffusion of hydrogen through La(Mg)CrO3 was found with a high activation energy. It was found that its electrical conductivity drops drastically, especially at low temperature, after exposure to hydrogen at high temperature. Also, the curvature of most of the conductivity plots, as well as the inability to observe the Hall effect, lends support to the proposal by Karim and Aldred that the small-polaron model which predicts thermally activated mobility is applicable to doped lanthanum chromite. From differential thermal analysis, an apparent absorption of hydrogen near 3000 C was noticed. Upon cooling the lanthanum chromite in hydrogen and subsequently reheating it in air, desorption occurred near 1700 C. The immediate purpose of this study was to determine whether hydrogen has a deleterious effect on lanthanum chromite in solid oxide fuel cells.

Solid solution barium–strontium chlorides with tunable ammonia desorption properties and superior storage capacity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bialy, Agata; Jensen, Peter B.; Center for Atomic-scale Materials Design, Department of Physics, Technical University of Denmark, Fysikvej 311, DK-2800 Kgs. Lyngby

Metal halide ammines are very attractive materials for ammonia absorption and storage—applications where the practically accessible or usable gravimetric and volumetric storage densities are of critical importance. Here we present, that by combining advanced computational materials prediction with spray drying and in situ thermogravimetric and structural characterization, we synthesize a range of new, stable barium-strontium chloride solid solutions with superior ammonia storage densities. By tuning the barium/strontium ratio, different crystallographic phases and compositions can be obtained with different ammonia ab- and desorption properties. In particular it is shown, that in the molar range of 35–50% barium and 65–50% strontium, stablemore » materials can be produced with a practically usable ammonia density (both volumetric and gravimetric) that is higher than any of the pure metal halides, and with a practically accessible volumetric ammonia densities in excess of 99% of liquid ammonia. - Graphical abstract: Thermal desorption curves of ammonia from Ba{sub x}Sr{sub (1−x)}Cl{sub 2} mixtures with x equal to 0.125, 0.25 and 0.5 and atomic structure of Sr(NH{sub 3}){sub 8}Cl{sub 2}. - Highlights: • Solid solutions of strontium and barium chloride were synthesized by spray drying. • Adjusting molar ratios led to different crystallographic phases and compositions. • Different molar ratios led to different ammonia ab-/desorption properties. • 35–50 mol% BaCl{sub 2} in SrCl{sub 2} yields higher ammonia density than any other metal halide. • DFT calculations can be used to predict properties of the mixtures.« less

Molecular dynamics simulations of energy dissipation and non-thermal diffusion on amorphous solid water.

PubMed

Fredon, A; Cuppen, H M

2018-02-21

Molecules in space are synthesized via a large variety of gas-phase reactions, and reactions on dust-grain surfaces, where the surface acts as a catalyst. Especially, saturated, hydrogen-rich molecules are formed through surface chemistry where the interstellar grains act as a meeting place and absorbing energy. Here we present the results of thousands of molecular dynamics simulations to quantify the outcome of an energy dissipation process. Admolecules on top of an amorphous solid water surface have been given translational energy between 0.5 and 5 eV. Three different surface species are considered, CO 2 , H 2 O and CH 4 , spanning a range in binding energies, number of internal degrees of freedom and molecular weight. The results are compared against a previous study using a crystalline water ice surface. Possible outcomes of a dissipation process are adsorption - possibly after long-range diffusion-, desorption and desorption of a surface molecule. The three admolecules were found to bind at different locations on the surface, particularly in terms of height. Water preferably binds on top of the surface, whereas methane fills the nanopores on the surface. This has direct consequences for desorption, travelled distance, and kick-out probabilities. The admolecules are found to frequently travel several tens of angstroms before stabilizing on a binding site, allowing follow-up reactions en route. We present kick-out probabilities and we have been able to quantify the desorption probability which depends on the binding energy of the species, the translational excitation, and a factor that accounts for difference in binding site height. We provide expressions that can be incorporated in astrochemical models to predict grain surface formation and return into the gas phase of these products.

Study on glass-forming ability and hydrogen storage properties of amorphous Mg{sub 60}Ni{sub 30}La{sub 10−x}Co{sub x} (x = 0, 4) alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lv, Peng; Wang, Zhong-min, E-mail: zmwang@guet.edu.cn; Zhang, Huai-gang

2013-12-15

Mg{sub 60}Ni{sub 30}La{sub 10−x}Co{sub x} (x = 0, 4) amorphous alloys were prepared by rapid solidification, using a melt-spinning technique. X-ray diffraction and differential scanning calorimetry analysis were employed to measure their microstructure, thermal stability and glass-forming ability, and hydrogen storage properties were studied by means of PCTPro2000. Based on differential scanning calorimetry results, their glass-forming ability and thermal stability were investigated by Kissinger method, Lasocka curves and atomic cluster model, respectively. The results indicate that glass-forming ability, thermal properties and hydrogen storage properties in the Mg-rich corner of Mg–Ni–La–Co system alloys were enhanced by Co substitution for La. Itmore » can be found that the smaller activation energy (ΔΕ) and frequency factor (υ{sub 0}), the bigger value of B (glass transition point in Lasocka curves), and higher glass-forming ability of Mg–Ni–La–Co alloys would be followed. In addition, atomic structure parameter (λ), deduced from atomic cluster model is valuable in the design of Mg–Ni–La–Co system alloys with good glass-forming ability. With an increase of Co content from 0 to 4, the hydrogen desorption capacity within 4000 s rises from 2.25 to 2.85 wt.% at 573 K. - Highlights: • Amorphous Mg{sub 60}Ni{sub 30}La{sub 10−x}Co{sub x} (x = 0 and 4) alloys were produced by melt spinning. • The GFA and hydrogen storage properties were enhanced by Co substitution for La. • With an increase of Co content, the hydrogen desorption capacity rises at 573 K.« less

TPD IR studies of CO desorption from zeolites CuY and CuX

NASA Astrophysics Data System (ADS)

Datka, Jerzy; Kozyra, Paweł

2005-06-01

The desorption of CO from zeolites CuY and CuX was followed by TPD-IR method. This is a combination of temperature programmed desorption and IR spectroscopy. In this method, the status of activated zeolite (before adsorption), the process of adsorption, and the status of adsorbed molecules can be followed by IR spectroscopy, and the process of desorption (with linear temperature increase) can be followed both by IR spectroscopy and by mass spectrometry. IR spectra have shown two kinds of Cu + sites in both CuY and CuX. Low frequency (l.f.) band (2140 cm -1 in CuY and 2130 cm -1 in CuX) of adsorbed CO represents Cu + sites for which π back donation is stronger and σ donation is weaker whereas high frequency h.f. band (2160 cm -1 in CuY and 2155 cm -1 in CuX) represent Cu + sites for which π back donation is weaker and σ donation is stronger. The TPD-IR experiments evidenced that the Cu + sites represented by l.f. band bond CO more weakly than those represented by h.f. one, indicating that σ donation has more important impact to the strength of Cu +-CO bonding. On the contrary, π back donation has bigger contribution to the activation of adsorbed molecules.

Desorption and sublimation kinetics for fluorinated aluminum nitride surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

King, Sean W., E-mail: sean.king@intel.com; 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) dilutedmore » 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.« less

Fragmentation as a condition for persistence - exploring a new perspective of mineral-organic interactions

NASA Astrophysics Data System (ADS)

Kleber, M.; Liu, S. Y.; Keiluweit, M.; Nico, P. S.; Ahmed, M.

2012-12-01

High radiocarbon ages (centennial to millennial) of soil organic matter tend to occur in soils with high proportions of reactive, hydroxylated minerals, including andisols, spodosols and oxisols. This indicates that the most reactive mineral surfaces, i.e. those that should in theory be particularly efficient in promoting transformations of organic matter are among the most powerful in protecting organic matter against decomposition on long time scales. The easiest way to reconcile this apparent paradox is to assume that organic compounds become fragmented upon contact with minerals, thereby generating fragmentation products which in turn are more likely to become preserved within the soil fabric than their precursor molecules. Here we use Vacuum Ultraviolet - Post Ionisation -Mass Spectroscopy (VUV-PI-MS) in combination with thermal and laser desorption to show how organic compounds undergo complete fragmentation upon contact with mineral surfaces. Fragmentation patterns were generally different between oxidic minerals and minerals belonging to the phyllosilicate group. Also, desorption from phyllosilicates generally required significantly higher energies than desorption from oxide phases. Our investigation suggests that, at low energy levels, breakdown and fragmentation is a probably major outcome of mineral-organic interactions. This observation supports a new model for the role of mineral-organic interactions in the preservation of organic compounds in the environment: mineral-induced fragmentation as a prerequisite for long term protection against decomposition.

Analysis of nitrogen-based explosives with desorption atmospheric pressure photoionization mass spectrometry.

PubMed

Kauppila, T J; Flink, A; Pukkila, J; Ketola, R A

2016-02-28

Fast methods that allow the in situ analysis of explosives from a variety of surfaces are needed in crime scene investigations and home-land security. Here, the feasibility of the ambient mass spectrometry technique desorption atmospheric pressure photoionization (DAPPI) in the analysis of the most common nitrogen-based explosives is studied. DAPPI and desorption electrospray ionization (DESI) were compared in the direct analysis of trinitrotoluene (TNT), trinitrophenol (picric acid), octogen (HMX), cyclonite (RDX), pentaerythritol tetranitrate (PETN), and nitroglycerin (NG). The effect of different additives in DAPPI dopant and in DESI spray solvent on the ionization efficiency was tested, as well as the suitability of DAPPI to detect explosives from a variety of surfaces. The analytes showed ions only in negative ion mode. With negative DAPPI, TNT and picric acid formed deprotonated molecules with all dopant systems, while RDX, HMX, PETN and NG were ionized by adduct formation. The formation of adducts was enhanced by addition of chloroform, formic acid, acetic acid or nitric acid to the DAPPI dopant. DAPPI was more sensitive than DESI for TNT, while DESI was more sensitive for HMX and picric acid. DAPPI could become an important method for the direct analysis of nitroaromatics from a variety of surfaces. For compounds that are thermally labile, or that have very low vapor pressure, however, DESI is better suited. Copyright © 2016 John Wiley & Sons, Ltd.

"Job-Sharing" Storage of Hydrogen in Ru/Li₂O Nanocomposites.

PubMed

Fu, Lijun; Tang, Kun; Oh, Hyunchul; Manickam, Kandavel; Bräuniger, Thomas; Chandran, C Vinod; Menzel, Alexander; Hirscher, Michael; Samuelis, Dominik; Maier, Joachim

2015-06-10

A "job-sharing" hydrogen storage mechanism is proposed and experimentally investigated in Ru/Li2O nanocomposites in which H(+) is accommodated on the Li2O side, while H(-) or e(-) is stored on the side of Ru. Thermal desorption-mass spectroscopy results show that after loading with D2, Ru/Li2O exhibits an extra desorption peak, which is in contrast to Ru nanoparticles or ball-milled Li2O alone, indicating a synergistic hydrogen storage effect due to the presence of both phases. By varying the ratio of the two phases, it is shown that the effect increases monotonically with the area of the heterojunctions, indicating interface related hydrogen storage. X-ray diffraction, Fourier transform infrared spectroscopy, and nuclear magnetic resonance results show that a weak LiO···D bond is formed after loading in Ru/Li2O nanocomposites with D2. The storage-pressure curve seems to favor H(+)/H(-) over H(+)/e(-) mechanism.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

Surface diffusion of hydrogen, deuterium and CO on Rh(111) has been investigated by laser-induced thermal desorption (LITD) and compared with previous results for these species on Pt(111) and on other metals. For deuterium in the coverage range 0.02 < theta < 0.33, the pre-exponential factor D/sub 0/ - 8 x 10/sup -2/ cm/sup 2//s, with a diffusion activation energy 3.7 < E/sub diff/ < 4.3 kcal/mol. For CO, E/sub diff/ = 7 kcal/mol, but D/sub 0/ rises from 10/sup -3/ to 10/sup -2/ cm/sup 2//s between theta = 0.01 and 0.40. Values of E/sub diff/ on different surfaces appear tomore » correlate with differences in heats of adsorption in different binding states which form saddle point configurations in surface diffusion. In addition, oxidation reactions on Rh and on several other transition metal surfaces may be limited to CO or H surface diffusion. 30 refs., 3 figs., 1 tab.« less

Helium retention behavior in simultaneously He+-H2+ irradiated tungsten

NASA Astrophysics Data System (ADS)

Zhou, Qilai; Azuma, Keisuke; Togari, Akihiro; Yajima, Miyuki; Tokitani, Masayuki; Masuzaki, Suguru; Yoshida, Naoaki; Hara, Masanori; Hatano, Yuji; Oya, Yasuhisa

2018-04-01

The purpose of this study is to elucidate helium (He) retention behavior in tungsten (W) under simultaneous He and hydrogen (H) irradiation. Polycrystalline-W was irradiated by He+ and H2+ simultaneously with the energy of 1.0 keV and 3.0 keV. He+ fluences were (0.5, 1.0, 10) × 1021 He+ m-2 and H2+ fluence was 1.0 × 1022 H+ m-2,respectively. After irradiation, He desorption behavior was investigated by high temperature thermal desorption spectroscopy (HT-TDS) in the temperature range of R.T.-1773 K. Micro-structure changes of W after irradiation were observed by TEM. It was found that simultaneous irradiation with different H2+ energy significantly changed He retention behavior. 1.0 keV H2+ suppressed the He bubble growth and no bubbles can be observed at room temperature. On the other hand, 3.0 keV H2+ facilitated the formation of He bubbles and increased the He retention due to the additional damage introduction by energetic H2+.

Deuterium trapping in the carbon-silicon co-deposition layers prepared by RF sputtering in D2 atmosphere

NASA Astrophysics Data System (ADS)

Zhang, Hongliang; Zhang, Weiyuan; Su, Ranran; Tu, Hanjun; Shi, Liqun; Hu, Jiansheng

2018-04-01

Deuterated carbon-silicon layers co-deposited on graphite and silicon substrates by radio frequency magnetron sputtering in pure D2 plasma were produced to study deuterium trapping and characteristics of the C-Si layers. The C-Si co-deposited layers were examined by ion beam analysis (IBA), Raman spectroscopy (RS), infrared absorption (IR) spectroscopy, thermal desorption spectroscopy (TDS) and scanning electron microscopy (SEM). It was found that the growth rate of the C-Si co-deposition layer decreased with increasing temperature from 350 K to 800 K, the D concentration and C/Si ratios increased differently on graphite and silicon substrates. TDS shows that D desorption is mainly as D2, HD, HDO, CD4, and C2D4 and release peaks occurred at temperatures of less than 900 K. RS and IR analysis reveal that the structure of the C-Si layers became more disordered with increasing temperatures. Rounded areas of peeling with 1-2 μm diameters were observed on the surface.

Sorption of phenanthrene and benzene on differently structural kerogen: important role of micropore-filling.

PubMed

Zhang, Yulong; Ma, Xiaoxuan; Ran, Yong

2014-02-01

Shale was thermally treated to obtain a series of kerogen with varied maturation. Their chemical, structural and porous properties were related to the sorption and/or desorption behaviors of phenanthrene and benzene. As the treatment temperature increases, aliphatic and carbonyl carbon of the kerogen samples decrease, while their aromaticity and maturation increase. Meanwhile, the isothermal nonlinearity of phenanthrene and benzene increases whereas the sorption capacity and micropore adsorption volumes (Vo,d) initially increase and then decrease. The Vo,d of benzene is significantly correlated with, but higher than that of phenanthrene, suggesting similar micropore filling mechanism and molecular sieve effect. The benzene desorption exhibits hysteresis, which is related to the pore deformation of the kerogen and the entrapment of solute in the kerogen matrix. The Vo,d of phenanthrene and benzene on the kerogen samples accounts for 23-46% and 36-65% of the maximum sorption volumes, respectively, displaying the importance of the micropore filling. Copyright © 2013 Elsevier Ltd. All rights reserved.

Cleaning techniques for applied-B ion diodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cuneo, M.E.; Menge, P.R.; Hanson, D.L.

Measurements and theoretical considerations indicate that the lithium-fluoride (LiF) lithium ion source operates by electron-assisted field-desorption, and provides a pure lithium beam for 10--20 ns. Evidence on both the SABRE (1 TW) and PBFA-II (20 TW) accelerators indicates that the lithium beam is replaced by a beam of protons, and carbon resulting from electron thermal desorption of hydrocarbon surface and bulk contamination with subsequent avalanche ionization. Appearance of contaminant ions in the beam is accompanied by rapid impedance collapse, possibly resulting from loss of magnetic insulation in the rapidly expanding and ionizing, neutral layer. Electrode surface and source substrate cleaningmore » techniques are being developed on the SABRE accelerator to reduce beam contamination, plasma formation, and impedance collapse. We have increased lithium current density a factor of 3 and lithium energy a factor of 5 through a combination of in-situ surface and substrate coatings, impermeable substrate coatings, and field profile modifications.« less

Synthesis of Ternary Borocarbonitrides by High Temperature Pyrolysis of Ethane 1,2-Diamineborane

PubMed Central

Leardini, Fabrice; Massimi, Lorenzo; Flores-Cuevas, Eduardo; Fernández, Jose Francisco; Ares, Jose Ramon; Betti, Maria Grazia; Mariani, Carlo

2015-01-01

Ethane 1,2-diamineborane (EDAB) is an alkyl-containing amine-borane adduct with improved hydrogen desorption properties as compared to ammonia borane. In this work, it is reported the high temperature thermolytic decomposition of EDAB. Thermolysis of EDAB has been investigated by concomitant thermogravimetry-differential thermal analysis-mass spectrometry experiments. EDAB shows up to four H2 desorption events below 1000 °C. Small fractions of CH4, C2H4 and CO/CO2 are also observed at moderate-high temperatures. The solid-state thermolysis product has been characterized by means of different structural and chemical methods, such as X-ray diffraction, Raman spectroscopy, Scanning electron microscopy, Elemental analysis, and X-ray photoelectron spectroscopy (XPS). The obtained results indicate the formation of a ternary borocarbonitride compound with a poorly-crystalline graphitic-like structure. By contrast, XPS measurements show that the surface is rich in carbon and nitrogen oxides, which is quite different to the bulk of the material. PMID:28793545

Ru sub 3 (CO) sub 12 and Mo(CO) sub 6 adsorbed on Ru(001) and Au/Ru: An infrared reflection-absorption study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Malik, I.J.; Hrbek, J.

1990-01-01

The authors obtained infrared reflection absorption (IRAS) and thermal desorption spectroscopy (TDS) data for Ru{sub 3}(CO){sub 12}/Ru(001) and Mo(CO){sub 6}/Au/Ru systems for metal carbonyl coverages between submonolayer and approximately 20 monolayers. They characterized the C-O stretching mode of both systems (4cm{sup {minus}1}FWHM) and a deformation mode of Mo(CO){sub 6} at 608cm{sup {minus}1} (1 cm{sup {minus}1}FWHM). Both IRAS and TDS data suggest adsorption and desorption of metal carbonyls as molecular species with a preferential orientation in the overlayers. The IR intensity of the C-O stretch per a C-O bond projected onto the surface normal is approximately twice (five times) larger formore » Ru{sub 3}(CO){sub 12} (Mo(CO){sub 6}) at submonolayer coverages than for CO/Ru(001) at {theta}{sub CO}=0.68.« less

Ru sub 3 (CO) sub 12 and Mo (CO) sub 6 overlayers adsorbed on Ru(001) and Au/Ru and their interaction with electrons and photons: An infrared reflection--absorption study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Malik, I.J.; Hrbek, J.

1991-05-01

We studied adsorbed Ru{sub 3}(CO){sub 12} and Mo (CO){sub 6} overlayers on Ru(001) and Au/Ru surfaces by infrared reflection--absorption spectroscopy (IRAS) and thermal desorption spectroscopy (TDS). We characterized the C--O stretching mode of both metal carbonyls (4 cm{sup {minus}1} FWHM) and a deformation mode of Mo (CO){sub 6} at 608 cm{sup {minus}1} with an unusually narrow FWHM of 1 cm{sup {minus}1}. Both IRAS and TDS data suggest adsorption and desorption of metal carbonyls as molecular species with a preferential orientation in the overlayers. We discuss annealing experiments of Ru{sub 3}(CO){sub 12}/Ru(001), the interaction of Ru{sub 3}(CO){sub 12} overlayers with electronsmore » of up to 100-eV energy, and the interaction of Mo (CO){sub 6} overlayers with 300-nm photons.« less