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At least 199 records · Page 11

Characterization of the Active Surface Species Responsible for UV-Induced Desorption of O2 from the Rutile TiO2(110) Surface

We have examined the chemical and photochemical properties of molecular oxygen on the (110) surface of rutile TiO2 at 100 K using electron energy loss spectroscopy (EELS), photon stimulated desorption (PSD) and scanning tunneling microscopy (STM). Oxygen chemisorbs on the TiO2(110) surface at 100 K through charge transfer from surface Ti3+ sites. The charge transfer process is evident in EELS by a decrease in the intensity of the Ti3+ d-to-d transition in EELS at ~0.9 eV and formation of a new loss ~2.8 eV. Based on comparisons with the available homogeneous and heterogeneous literature for complexed/adsorbed O2, the species responsible for the 2.8 eV peak can be assigned to a surface peroxo (O2 2-) state of O2. This species was identified as the active form of adsorbed O2 on TiO2(110) for PSD. The adsorption site of this peroxo species was assigned to that of a regular five-cooridinated Ti4+ (Ti5c) site based on comparisons between the UV exposure dependent behavior of O2 in STM, PSD and EELS data. Assignment of the active form of adsorbed O2 to a peroxo species at normal Ti5c sites necessitates reevaluation of the simple mechanism in which a single valence band hole neutralizes a singly charged O2 species (superoxo or O2-) leading to desorption of O2 from a physisorbed potential energy surface. This work was supported by the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, and the Chemical Imaging Initiative at Pacific Northwest National Laboratory (PNNL), and was performed in the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE's Office of Biological and Environmental Research and located at PNNL.

Environmental Molecular Sciences Laboratory↗

Hydrogen desorption from the surface and subsurface of cobalt

The influence of coverage on the diffusion of hydrogen into the subsurface of cobalt was studied using density functional theory (DFT) and temperature programmed desorption (TPD). DFT calculations show that as the hydrogen coverage on Co(0001) increases, the barrier for hydrogen diffusion into the bulk decreases by 20%. Additionally, subsurface hydrogen on a hydrogen covered surface was found to be more stable when compared to a clean cobalt surface. To test these theoretical findings experimentally, excited hydrogen was used in an ultra-high vacuum environment to access higher hydrogen coverages. Here, our TPD studies showed that at high hydrogen coverages, a sharp low temperature feature appeared, indicating the stabilization of subsurface hydrogen. Further DFT calculations indicate that this sharp low temperature feature results from associative hydrogen desorption from a hydrogen saturated surface with a population of subsurface hydrogen. Microkinetic modelling was used to model the TPD spectra for hydrogen desporption from cobalt with and without subsurface hydrogen, showing reasonable agreement with experiment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Coverage-dependent adsorption and desorption of oxygen on Pd(100)

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 intermediate 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.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Symmetry-resolved CO desorption and oxidation dynamics on O/Ru(0001) probed at the C K-edge by ultrafast X-ray spectroscopy

In this work, we report on carbon monoxide desorption and oxidation induced by 400 nm femtosecond laser excitation on the O/Ru(0001) surface probed by time-resolved X-ray absorption spectroscopy (TR-XAS) at the carbon K-edge. The experiments were performed under constant background pressures of CO (6x10 -8 Torr) and O 2 (3x10 -8 Torr). Under these conditions, we detect two transient CO species with narrow 2π* peaks, suggesting little 2π* interaction with the surface. Based on polarization measurements, we find that these two species have opposing orientations: (1) CO favoring a more perpendicular orientation and (2) CO favoring a more parallel orientation with respect to the surface. We also directly detect gas-phase CO 2 using a mass spectrometer and observe weak signatures of bent adsorbed CO 2 at slightly higher X-ray energies than the 2π* region. These results are compared to previously reported TR-XAS results at the O K-edge where the CO background pressure was three times lower (2x10 -8 Torr) while maintaining the same O 2 pressure. At the lower CO pressure, in the CO 2π* region, we observed adsorbed CO and a distribution of OC-O bond lengths close to the CO oxidation transition state, with little indication of gas-like CO. The shift towards 'gas-like' CO species may be explained by the higher CO exposure, which blocks O adsorption, decreasing O coverage and increasing CO coverage. These effects decrease the CO desorption barrier through dipole-dipole interaction, while simultaneously increasing the CO oxidation barrier.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Upscaling of U(VI) Desorption and Transport from Decimeter-Scale Heterogeneity to Plume-Scale Modeling

Scientifically defensible predictions of field scale U(VI) transport in groundwater requires an understanding of key processes at multiple scales. These scales range from smaller than the sediment grain scale (less than 10 μm) to as large as the field scale which can extend over several kilometers. The key processes that need to be considered include both geochemical reactions in solution and at sediment surfaces as well as physical transport processes including advection, dispersion, and pore-scale diffusion. The research summarized in this report includes both experimental and modeling results in batch, column and tracer tests. The objectives of this research were to: (1) quantify the rates of U(VI) desorption from sediments acquired from a uranium contaminated aquifer in batch experiments;(2) quantify rates of U(VI) desorption in column experiments with variable chemical conditions, and(3) quantify nonreactive tracer and U(VI) transport in field tests.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Measurement of Passive Uptake Rates for Volatile Organic Compounds on Commercial Thermal Desorption Tubes and the Effect of Ozone on Sampling

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 stirred 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.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Dynamic Moisture Sorption and Desorption in Fumed Silica-filled Silicone Foam

Characterizing dynamic moisture sorption and desorption in fumed silica-filled silicone foam is necessary for determining material compatibilities and life predictions, particularly in sealed environments that may be exposed to a range of environmental conditions. Thermogravimetric analysis (TGA) and near infrared spectroscopy (NIR) were performed on S5470 fumed silica-filled silicone foam to determine the weight percent of moisture at saturation. Additionally, TGA was used to determine the time, temperature, and relative humidity levels required for sorption and desorption of physisorbed moisture in S5470.

36 MATERIALS SCIENCE↗

Elucidating Hydrogen Reaction-Induced Water Desorption from Oxide-Passivated Metal Surfaces for Plasma Applications

Elucidating the mechanisms responsible for sub-microsecond desorption of water and other impurities from electrode surfaces at high heating rates is crucial for understanding pulsed power behavior. Ionization of desorbed impurities in the vacuum regions causes power or current loss; devising methods to limit such desorption during the short time scale of pulsed power is needed to improve corresponding applications. Previous molecular modeling studies have strongly suggested that, under high vacuum conditions, the amount of water impurity desorbing from oxide surfaces on metal electrodes is at a sub-monolayer level at room temperature, which appears insufficient to explain observed pulsed power energy losses at high current densities. In this work, we apply Density Functional Theory (DFT) techniques to show that hydrogen trapped inside iron metal can diffuse into hematite (α-Fe 2 O 3 ) on the metal surface, ultimately reacting with the oxide to form Fe(II) and H 2 O. The latter desorbs at elevated temperature and may explain the anomalous amount of desorbed impurity inferred from pulsed-power experiments. We also apply a suite of characterization techniques to demonstrate that when iron metal is heated to 650 °C, the dominant surface oxide component becomes α-Fe 2 O 3 . The oxide facets exposed are found to be a mixture of (0001), (10-10), and others, in agreement with the DFT models used.

74 ATOMIC AND MOLECULAR PHYSICS↗

Desorption Kinetics and Binding Energies of Small Hydrocarbons

Small hydrocarbons are a vital organic reservoir in protostellar and protoplanetary environments. Constraints on desorption temperatures and binding energies of such hydrocarbons are essential for accurate predictions of where these molecules exist in the ice versus gas phase during the different stages of star and planet formation. Here, through a series of temperature programmed desorption experiments, we constrain the binding energies of 2- and 3-carbon hydrocarbons (C 2 H 2 —acetylene, C 2 H 4 —ethylene, C 2 H 6 —ethane, C 3 H 4 —propyne, C 3 H 6 —propene, and C 3 H 8 —propane) to 2200–4200 K in the case of pure amorphous ices, to 2400–4400 K on compact amorphous H 2 O, and to 2800–4700 K on porous amorphous H 2 O. The 3-carbon hydrocarbon binding energies are always larger than the 2-carbon hydrocarbon binding energies. Within the 2- and 3-carbon hydrocarbon families, the alkynes (i.e., least-saturated) hydrocarbons exhibit the largest binding energies, while the alkane and alkene binding energies are comparable. Binding energies are ~5%–20% higher on water ice substrates compared to pure ices, which is a small increase compared to what has been measured for other volatile molecules such as CO and N 2 . Thus in the case of hydrocarbons, H 2 O has a less pronounced effect on sublimation front locations (i.e., snowlines) in protoplanetary disks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The application of diffusion theory to the analysis of hydrogen desorption data at 25 deg C

The application of diffusion theory to the analysis of hydrogen desorption data (coulombs of H2 desorbed versus time) has been studied. From these analyses, important information concerning hydrogen solubilities and the nature of the hydrogen distributions in the metal has been obtained. Two nickel base alloys, Rene' 41 and Waspaloy, and one ferrous alloy, 4340 steel, are studied in this work. For the nickel base alloys, it is found that the hydrogen distributions after electrolytic charging conforms closely to those which would be predicted by diffusion theory. For Waspaloy samples charged at 5,000 psi, it is found that the hydrogen distributions are essentially the same as those obtained by electrolytic charging. The hydrogen distributions in electrolytically charged 4340 steel, on the other hand, are essentially uniform in nature, which would not be predicted by diffusion theory. A possible explanation has been proposed. Finally, it is found that the hydrogen desorption is completely explained by the nature of the hydrogen distribution in the metal, and that the fast hydrogen is not due to surface and sub-surface hydride formation, as was originally proposed.

Danford, M. D.↗

Diffusion Analysis Of Hydrogen-Desorption Measurements

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.

Danford, Merlin D.↗

Continuous electron stimulated desorption using a ZrO2/Ag permeation membrane

During the development of an atomic oxygen beam generator for laboratory simulation of the atmospheric conditions in low earth orbit, a new technique for performing electron stimulated desorption (ESD) in a continuous manner has been developed. In this technique, oxygen permeates through an Ag membrane at elevated temperature thereby providing a continuous supply of oxygen atoms to the 1000-A ZrO2 coating at the vacuum interface. ESD then results in a large peak of neutral O2 molecules which ultimately decay into steady-state desorption. The ESD signal is linear with respect to primary beam flux (0.035 O2 molecules per electron at a primary beam energy of 1 keV) but nonlinear with respect to primary beam energy.

Outlaw, R. A.↗

Explosive desorption of icy grain mantles in dense clouds

The cycling of the condensible material in dense clouds between the gas phase and the icy grain mantles is investigated. In the model studied, desorption of the ice occurs due to grain mantle explosions when photochemically stored energy is released after transient heating by a cosmic ray particle. It is shown that, depending on the grain size distribution in dense clouds, explosive desorption can maintain up to about eight percent of the carbon in the form of CO in the gas phase at typical cloud densities.

Schutte, W. A.↗

Characterization of polymer decomposition products by laser desorption mass spectrometry

Laser desorption mass spectrometry has been used to characterize the ash-like substances formed on the surfaces of polymer matrix composites (PMC's) during exposure on LDEF. In an effort to minimize fragmentation, material was removed from the sample surfaces by laser desorption and desorbed neutrals were ionized by electron impact. Ions were detected in a time-of-flight mass analyzer which allows the entire mass spectrum to be collected for each laser shot. The method is ideal for these studies because only a small amount of ash is available for analysis. Three sets of samples were studied including C/polysulfone, C/polyimide and C/phenolic. Each set contains leading and trailing edge LDEF samples and their respective controls. In each case, the mass spectrum of the ash shows a number of high mass peaks which can be assigned to fragments of the associated polymer. These high mass peaks are not observed in the spectra of the control samples. In general, the results indicate that the ash is formed from decomposition of the polymer matrix.

Pallix, Joan B.↗

Collisional desorption of NO by fast O atoms

Surface-adsorbed NO figures largely in the mechanism that produces visible glow around spacecraft in low Earth orbit (LEO). In view of the potential interference to optical observations such a glow represents, we have investigated the collision-induced desorption of NO from Al, Ni, and Z306 Chemglaze-coated surfaces at 96 K by hyperthermal (8 km/s) oxygen atoms. The removal of surface NO was followed by the monitoring of the visible fluorescence of electronically excited NO2 produced through the surface-mediated reaction O + NO. A variability in collisional desorption rate with material was observed. The limited data suggest a removal efficiency of 4 to 8% of the impinging O atom flux. Implications for the atmospheric scouring of contaminants from external surfaces of LEO spacecraft are discussed.

Sonnenfroh, David M.↗

Thermal Desorption of Tritium from Fluoride Salt-Cooled Reactor Materials

The fluoride-salt-cooled high-temperature reactor (FHR) is a high-temperature fission reactor concept involving a liquid fluoride salt coolant, coated particle fuel, and enhanced passive safety mechanisms. Utilizing a low-pressure coolant and high temperature fuel allows for smaller reactor buildings and use of gas Brayton power cycles for higher efficiency in electricity production. One of the fluoride salts being considered for the FHR coolant is 2LiF - BeF{sub 2} (flibe). Tritium is generated frequently in flibe from thermal neutron transmutation of Li-6 and Be-9. Tritium retention in irradiated structural materials presents a challenge to the design of the FHR; high neutron fluence can induce significant material damage and alteration of microstructures to trap tritium in the structure, particularly in carbon-based materials (such as steels). Investigation of tritium transport in flibe salt and structural materials is also critical to evaluating mass balance of tritium in a system for quantifying leakage of tritium to the environment. It is important to understand the uptake of tritium in these proposed core materials since the transport of tritium within an FHR is of critical concern for operational safety due to corrosion, and to prevent tritium release into the environment. The presence of TF corrodes stainless steel by oxidizing chromium. Tritium gas (T{sub 2}) easily diffuses through reactor materials and can be released into the environment through the primary piping and heat exchangers. There is great interest in identifying materials that are compatible with the FHR environment that can be used to getter tritium from the salt, or to inhibit the diffusion of tritium to prevent its release into the environment. As part of the FHR Integrated Research Project (IRP), capsules containing proposed core materials immersed in flibe salt were irradiated at 700 deg. C for 1000 hours (FS-1) and 300 hours (FS-2) in the MIT Research Reactor (MITR). During irradiation, tritium is produced in the salt, and then interacts with the other materials in the capsule. Measurements of the effluent gas during the FHR IRP irradiation experiments indicated that less than 1% of the tritium generated in the salt escaped in the gas phase. It is assumed that most of the tritium was captured, either via diffusion or surface adsorption, on the materials inside the capsule. Tritium frequently adsorbs to sample surfaces in the form of HTO, which requires relatively low temperatures to release (on the order of 100 deg. C). In certain cases, tritium can be bound in the bulk of materials from diffusion or neutron transmutation of lithium and beryllium in the structural materials. Accurate measurement of very small concentrations of hydrogen is difficult; by taking advantage of the radioactive decay of tritium (which emits low-energy beta radiation), several methods become available to detect and quantitatively measure the tritium. The most sensitive method is liquid scintillation counting (LSC), which requires the tritium to be suspended in optically-transparent liquid media that is compatible with scintillating solution, such as water. This measurement technique requires the tritium to be extracted from the material, which can be achieved through leaching into water, thermal desorption, or complete destruction of the sample by acid digestion or pyrolysis. A less destructive method is preferred in order to preserve the specimens, reduce the generation of radioactive mixed wastes, and minimize the carryover of other activation products. For total thermal desorption of tritium from the materials, the tritiated materials must be heated to temperatures in excess of 300 deg. C. Heating the specimens above the irradiation temperature will re-mobilize the tritium and allow it to be captured from the gas stream directly into LSC media. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Chemical Characterization of Crude Petroleum Using Nanospray Desorption Electrospray Ionization Coupled with High-Resolution Mass Spectrometry

Nanospray desorption electrospray ionization (nano-DESI) combined with high-resolution mass spectrometry was used for the first time for the analysis of liquid petroleum crude oil samples. The analysis was performed in both positive and negative ionization modes using three solvents one of which (acetonitrile/toluene mixture) is commonly used in petroleomics studies while two other polar solvents (acetonitrile/water and methanol/water mixtures) are generally not compatible with petroleum characterization using mass spectrometry. The results demonstrate that nano-DESI analysis efficiently ionizes petroleum constituents soluble in a particular solvent. When acetonitrile/toluene is used as a solvent, nano-DESI generates electrospray-like spectra. In contrast, strikingly different spectra were obtained using acetonitrile/water and methanol/water. Comparison with the literature data indicates that these solvents selectively extract water-soluble constituents of the crude oil. Water-soluble compounds are predominantly observed as sodium adducts in nano-DESI spectra indicating that addition of sodium to the solvent may be a viable approach for efficient ionization of water-soluble crude oil constituents. Nano-DESI enables rapid screening of different classes of compounds in crude oil samples using solvents that are rarely used for petroleum characterization.

02 PETROLEUM↗