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At least 595 records · Page 33

Optical and mass-spectral characterization of mixed-gas flowing atmospheric-pressure afterglow sources

Plasma-based ambient desorption/ionization (ADI) sources for mass spectrometry (MS) often use helium as the primary discharge gas due to the large reaction cross section of excited helium species with atmospheric gases, which ultimately leads to efficient reagent-ion formation. However, some studies have shown that mixed-gas plasmas provide unique advantages. For instance, our group showed that a helium-oxygen flowing atmospheric-pressure afterglow (He:O 2 -FAPA) source yielded enhanced ion signals for small polar analytes, but compounds with aromatic rings underwent chemical modification to produce pyrylium species. Here, it is shown that the addition of H 2 to the helium FAPA gas significantly decreased the reagent-ion signals, but analyte-ion signal was not affected to the same degree. In addition, mass spectra obtained with He:H 2 -FAPA were chemically cleaner with fewer ions stemming from analyte species and produced less oxidation of analytes. Addition of nitrogen increased the abundance of negative reagent ions (e.g., NO 2 - and NO 3 - ) which led to enhanced ion signal for RDX. To better understand these unique advantages of a mixed-gas FAPA, the impact of molecular-gas (O 2 , N 2 , or H 2 ) addition on the optical-emission spectra from the discharge was also measured. Spatially resolved emission was obtained from the anode- and negative-glow regions. In general, addition of small fractions (~0.1%) of molecular gases decreased helium and OH emission intensities. Atomic oxygen and hydrogen emission increased with the addition of O 2 and H 2 , respectively. Furthermore, emission characteristics of N 2 , N 2 + , and NO with respect to molecular gas composition on He-FAPA were measured. Finally, fundamental plasma parameters, such as OH rotational temperature (T rot ), were also calculated for these mixed-gas systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Gas Permeation and Separation Characteristics of Microporous TpHz COF Membranes Synthesized by Substrate-Assisted Interfacial Polymerization

Microporous two-dimensional covalent organic framework (2D COF) membranes offer promise for gas separation applications, but their gas transport mechanism remains unclear. In this study, a TpHz 2D COF membrane supported on a macroporous nylon substrate is prepared by substrate-assisted interfacial polymerization under mild conditions. The formation of a continuous and dense thin (~300 nm thick) TpHz layer is confirmed by scanning electron microscopy and Fourier transform infrared spectroscopy. Characterization by X-ray diffraction, grazing incidence wide-angle X-ray scattering, and N 2 porosimetry qualitatively reveals the microstructures of the supported TpHz membranes, i.e., they comprise partially oriented 2D COF lamellar crystallites with moderate crystallinity in an eclipsed (AA) stacking geometry, centering the effective membrane pore size distribution at ~1.1 nm. Further, single gas permeation data show that the transport of common molecular gases, including H 2 , He, CH 4 , N 2 , and CO 2 , through the synthesized TpHz membranes follows the Knudsen transport mechanism, where single gas permeance decreases with an increasing molecular weight and permeation temperature. Binary gas separation results show that in the equimolar CO 2 /N 2 mixture, the presence of the CO 2 surface flow slightly hinders the N 2 flow at room temperature due to the reduced membrane channel size by the adsorbed CO 2 gas layer on TpHz’s pore wall. In contrast, permeation of the equimolar CH 4 /N 2 binary mixture does not exhibit a discernible surface flow of both gases due to their much lower gas uptake on TpHz, and their transport mechanism follows Knudsen-like behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Subdiffusive High-Pressure Hydrogen Gas Dynamics in Elastomers

We report elastomeric rubber materials serve a vital role as sealing materials in the hydrogen storage and transport infrastructure. With applications including O-rings and hose liners, these components are exposed to pressurized hydrogen at a range of temperatures, cycling rates, and pressure extremes. High-pressure exposure and subsequent rapid decompression often lead to cavitation and stress-induced damage of the elastomer due to localization of the hydrogen gas. Here, we use all-atom classical molecular dynamics simulations to assess the impact of compositional variations on gas diffusion within the commonly used elastomer ethylene–propylene–diene monomer (EPDM). With the aim to build a predictive understanding of precursors to cavitation and to motivate material formulations that are less sensitive to hydrogen-induced failure, we perform systematic simulations of gas dynamics in EPDM as a function of temperature, gas concentration, and cross-link density. Our simulations reveal anomalous, subdiffusive hydrogen motion at pressure and intermediate times. We identify two groups of gas with different mobilities: one group exhibiting high mobility and one group exhibiting low mobility due to their motion being impeded by the polymer. With decreasing temperatures, the low-mobility group shows increased gas localization, the necessary precursor for cavitation damage in these materials. At lower temperatures, increasing cross-link density led to greater hydrogen gas mobility and a lower fraction of caged hydrogen, indicating that increasing cross-link density may reduce precursors to cavitation. Finally, we use a two-state kinetic model to determine the energetics associated with transitions between these two mobility states.

36 MATERIALS SCIENCE↗

When Photoelectrons Meet Gas Molecules: Determining the Role of Inelastic Scattering in Ambient Pressure X-ray Photoelectron Spectroscopy

Inelastic photoelectron scattering (IPES) by gas molecules, a critical phenomenon observed in ambient pressure X-ray photoelectron spectroscopy (APXPS), complicates spectral interpretation due to kinetic energy loss in the primary spectrum and the appearance of additional features at higher binding energies. In this study, we systematically investigate IPES in various gas environments using APXPS, providing detailed insights into interactions between photoelectrons emitted from solid surfaces and surrounding gas molecules. Corelevel XPS spectra of Au, Ag, Zn, and Cu metals were recorded over a wide kinetic energy range in the presence of CO 2 , N 2 , Ar, and H 2 gases, demonstrating the universal nature of IPES across different systems. Additionally, we analyzed spectra of scattering effects induced by gas-phase interactions without metal solids. In two reported CO 2 -reduction systems (p-GaN/ Au/Cu and p-Si/TaO x /Cu), we elucidated that IPES is independent of the composition, structure, or size of the solid materials. Using metal foil platforms, we further developed an analytical model to extract electron excitation cross sections of gas molecules. These findings enhance our understanding of IPES mechanisms and enable the predictions of IPES structures in other solid–gas systems, providing a valuable reference for future APXPS studies and improving the accuracy of spectral analysis in gas-rich catalytic interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Viscous Dissipation and Apparent Permeability of Gas Flow in Nanoporous Media

The nanopore confinement effect can increase the mobility for gas flow in shale rocks, and the apparent permeability is usually adopted to account for this effect. However, most of the apparent permeability calculation models are derived based on straight channels (capillaries) and neglect the influence of end effect. The end effect is caused by the bending of streamlines which yields more viscous dissipation and additional flow resistance for gas flow in nanoporous media. Here, for the first time the viscous dissipation for gas flow in nanoporous media is analyzed. In addition, an improved apparent permeability calculation model is proposed based on the Beskok-Karniadakis (B-K) model by introducing the influence of end effect, which is characterized by the ratio of the length to the width of a short channel (L/H). The accuracy of this model is validated by lattice Boltzmann simulations of gas flow in three different geometries: an infinite-length straight channel, a finite-length straight channel, and nanoporous media. For the infinite-length straight channel, there is no end effect therefore both the B-K model and the improved model can well predict the apparent permeability. However, for the finite-length straight channel and nanoporous media, the original B-K model overestimates the gas apparent permeability as it neglects the influence of end effect, while the improved model can still well predict the gas apparent permeability. In summary, the improved apparent permeability calculation model is more reasonable in predicting gas mobility in nanoporous media.

58 GEOSCIENCES↗

Changes in Physical Properties of Everglades Peat Soils Induced by Increased Salinity at the Laboratory Scale: Implications for Changes in Biogenic Gas Dynamics

Abstract Saltwater intrusion due to sea level rise is a major concern for the Florida Everglades because it may induce shifts in ecosystem productivity and physical soil properties. However, the effects of saline water intrusion into the current carbon gas dynamics of the Everglades (particularly in terms of biogenic gas production and emissions, i.e., CH 4 and CO 2 ) are still uncertain. In this work, we present a laboratory‐based study to simulate how sea level rise may alter the physical properties (i.e., hydraulic conductivity) of peat soils from the Everglades and consequently affect the accumulation and release of biogenic gases within the peat matrix. Peat monoliths collected from the Everglades were subjected to progressive increases in salinity from a NaCl solution, and changes to the biogenic gas dynamics regime were simultaneously monitored using a combination of time‐lapse ground‐penetrating radar measurements, manometers, time‐lapse photography, and gas traps. Physical changes to the peat matrix at each salinity interval were assessed using constant head permeameter tests. Consistent with previous research, results show that a progressive increase in salinity (from fresh to saltwater) results in (1) a progressive increase in hydraulic conductivity and (2) a progressive decrease in gas content within the peat matrix (i.e., production) and gas releases. This work has implications for better understanding the potential effects of saltwater intrusion into freshwater peatland systems in the Everglades, particularly in terms of carbon gas dynamics.

Sirianni, Matthew J.↗

Molecular bridge-mediated ultralow-power gas sensing

Abstract We report the electrical detection of captured gases through measurement of the quantum tunneling characteristics of gas-mediated molecular junctions formed across nanogaps. The gas-sensing nanogap device consists of a pair of vertically stacked gold electrodes separated by an insulating 6 nm spacer (~1.5 nm of sputtered α-Si and ~4.5 nm ALD SiO 2 ), which is notched ~10 nm into the stack between the gold electrodes. The exposed gold surface is functionalized with a self-assembled monolayer (SAM) of conjugated thiol linker molecules. When the device is exposed to a target gas (1,5-diaminopentane), the SAM layer electrostatically captures the target gas molecules, forming a molecular bridge across the nanogap. The gas capture lowers the barrier potential for electron tunneling across the notched edge region, from ~5 eV to ~0.9 eV and establishes additional conducting paths for charge transport between the gold electrodes, leading to a substantial decrease in junction resistance. We demonstrated an output resistance change of >10 8 times upon exposure to 80 ppm diamine target gas as well as ultralow standby power consumption of <15 pW, confirming electron tunneling through molecular bridges for ultralow-power gas sensing.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

A Novel Relative Permeability Model for Gas and Water Flow in Hydrate-Bearing Sediments With Laboratory and Field-Scale Application

In a producing gas hydrate reservoir the effective porosity available for fluid flow constantly changes with dissociation of gas hydrate. Therefore, accurate prediction of relative permeability using legacy models (e.g. Brooks-Corey (B-C), van Genuchten, etc.) that were developed for conventional oil and gas reservoirs would require empirical parameters to be calibrated at various S h over its range of variation, but such calibrations are precluded because of lack of experimental relative permeability data. This study proposes a new relative permeability model for gas hydrate-bearing media that is a function of maximum capillary pressure, capillary entry pressure, pore size distribution index, residual saturations, hydrate saturation, and four other constants. The three novel features of the proposed model are: (i) requires fitting its six empirical parameters only once using experimental data from any single S h , and the same set of empirical parameters predict relative permeability at all S h , (ii) includes the effect of capillarity, and (iii) includes the effect of pore-size distribution. From practical standpoint, the model can be used to simulate multiphase flow in gas hydrate-bearing sediments where the proposed relative permeability can account for the evolving hydrate saturation. The proposed model is implemented in a numerical simulator and the wall time required to perform simulations using the proposed model is shown to be similar to the time it takes to run same simulations with the B-C model. The proposed model is a step forward towards achieving the goal of physically accurate modeling of multiphase flow for gas hydrate-bearing sediments that accounts for the effect of gas hydrate saturation change on relative permeability.

54 ENVIRONMENTAL SCIENCES↗

The role of gas flow distributions on CO 2 mineralization within monolithic cemented composites: coupled CFD-factorial design approach

The carbonation kinetics of monolithic cementing composites are strongly affected by gas transport which is, in turn, influenced by microstructural resistances and the presence of liquid water within pore networks. The non-uniform gas flow distribution within the CO 2 mineralization reactor can impart mass transfer resistance in the monolith microstructure, which affects the uptake of CO 2 (“carbonation”) of the cementing composites. This paper demonstrates how the gas spatial distribution (velocity and flow rate; quantified by CFD analysis) and processing conditions (temperature, relative humidity, and flow rate; quantified by factorial design) affect drying and carbonation, and in turn, the engineering properties of a representative ‘monolithic’ carbonate-cemented concrete component (i.e., herein concrete masonry unit: CMUs, also known as concrete block). It is shown that the gas flow distribution affects drying front penetration and results in moisture and carbonation gradients within the monolith. Particularly, variations in drying kinetics caused by non-uniformity of the contacting gas velocity impose gradients in moisture saturation, which results in increasing microstructural resistance to CO 2 transport. The resultant non-uniform carbonate-mineral formation (i.e., carbonate cementation), if not controlled, can produce gradients in mechanical properties and may alter failure patterns upon loading. Finally, these insights inform the optimal design of gas flow distribution systems and processing conditions within CO 2 mineralization reactors for the manufacturing of low-CO 2 concrete components using CO 2 -dilute industrial flue gas streams.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Transitions between electron emission and gas breakdown mechanisms across length and pressure scales

This Perspective outlines theoretical, simulation, and experimental studies linking electron emission and gas breakdown. Many studies have investigated field emission-driven microscale gas breakdown, including recent reviews [Garner et al., IEEE Trans. Plasma Sci. 48, 808–824 (2020); Fu et al., Plasma Res. Express 2, 013001 (2020)]. This Perspective focuses on generalizing field emission-driven microscale gas breakdown to consider the contribution of other forms of electron emission, specifically thermionic and space-charge limited. Recent theoretical studies have unified thermionic, field, and space-charge limited emission with and without collisions to derive “nexuses” where the individual solutions match, indicating transitions in the mechanisms. Reducing device size to nanoscale at atmospheric pressure leads to a transition from field emission to space-charge limited emission for nitrogen at ~250 nm. This Perspective summarizes the derivation of these nexuses and future extensions. We next describe simulation and theoretical studies for field emission-driven microscale gas breakdown and highlight how the nexus theory may be integrated to account for temperature, space-charge, and pulse parameters. Finally, we summarize the development of optical techniques to assess microscale gas breakdown and recent nanoscale experiments at atmospheric pressure that suggest that space-charge may begin to contribute to field emission prior to gas breakdown. We highlight the combination of theory, simulation, and experiment to link electron emission and gas breakdown mechanisms across length, pressure, and temperature scales for applications that include vacuum electronics, pulsed power, and medicine.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Lasergate: A windowless gas target for enhanced laser preheat in magnetized liner inertial fusion

At the Z Facility at Sandia National Laboratories, the magnetized liner inertial fusion (MagLIF) program aims to study the inertial confinement fusion in deuterium-filled gas cells by implementing a three-step process on the fuel: premagnetization, laser preheat, and Z-pinch compression. In the laser preheat stage, the Z-Beamlet laser focuses through a thin polyimide window to enter the gas cell and heat the fusion fuel. However, it is known that the presence of the few μm thick window reduces the amount of laser energy that enters the gas and causes window material to mix into the fuel. These effects are detrimental to achieving fusion; therefore, a windowless target is desired. The Lasergate concept is designed to accomplish this by “cutting” the window and allowing the interior gas pressure to push the window material out of the beam path just before the heating laser arrives. In this work, we present the proof-of-principle experiments to evaluate a laser-cutting approach to Lasergate and explore the subsequent window and gas dynamics. Further, an experimental comparison of gas preheat with and without Lasergate gives clear indications of an energy deposition advantage using the Lasergate concept, as well as other observed and hypothesized benefits. While Lasergate was conceived with MagLIF in mind, the method is applicable to any laser or diagnostic application requiring direct line of sight to the interior of gas cell targets.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Gas hydrate quantification in Walker Ridge block 313, Gulf of Mexico, from full-waveform inversion of ocean-bottom seismic data

The Gulf of Mexico (GOM) Joint Industry Project Leg 2 logging-while-drilling data in Walker Ridge lease block 313 (WR313) in the GOM detected gas hydrate in coarse- and fine-grained sediments at sites WR313-G and WR313-H. The coarse-grained units are thin ([Formula: see text]) and highly saturated, whereas the fine-grained unit is thick (approximately 200 m) with low saturation and fracture-filling gas hydrate. Unlike its coarse-grained counterpart, the seismic character of the fine-grained unit does not clearly indicate the presence of gas hydrate, which would likely have remained undiscovered in the absence of drilling. In this paper, through frequency-domain acoustic full-waveform inversion (FWI) of ocean-bottom seismometer data along a 2D multichannel seismic transect near sites WR313-G and WR313-H, we detect and quantify gas hydrate in the fine-grained unit. Key results are as follows: First, the base of the gas hydrate stability zone, which is not obvious in the reflection profile, can be discerned in the FWI results. Second, the gas hydrate in the fine-grained unit is mainly confined to the area between two sets of opposite-dipping normal faults implying that the fault architecture may be partially responsible for this gas hydrate accumulation and distribution.

Geochemistry & Geophysics↗

End-Use Savings Shapes Measure Documentation: Boiler Replacement with Air-Source Heat Pump Boiler and Natural Gas Boiler Backup

Building on the successfully completed effort to calibrate and validate the U.S. Department of Energy's ResStock (™) and ComStock (™) models over the past three years, the objective of this work is to produce national data sets that empower analysts working for federal, state, utility, city, and manufacturer stakeholders to answer a broad range of analysis questions. The goal of this work is to develop energy efficiency, electrification, and demand flexibility end-use load shapes (electricity, gas, propane, or fuel oil) that cover a majority of the high-impact, market-ready (or nearly market-ready) measures. "Measures" refers to energy efficiency variables that can be applied to buildings during modeling. An end-use savings shape is the difference in energy consumption between a baseline building and a building with an energy efficiency, electrification, or demand flexibility measure applied. It results in a time-series profile that is broken down by end use and fuel (electricity or on-site gas, propane, or fuel oil use) at each timestep. ComStock is a highly granular, bottom-up model that uses multiple data sources, statistical sampling methods, and advanced building energy simulations to estimate the annual subhourly energy consumption of the commercial building stock across the United States. The baseline model intends to represent the U.S. commercial building stock as it existed in 2018. The methodology and results of the baseline model are discussed in the final technical report of the End-Use Load Profiles project. This documentation focuses on a single end-use savings shape measure - boiler replacement with air-source heat pump boiler with natural gas boiler backup. This measure replaces natural gas boilers for HVAC application by air-source heat pump boilers when applicable and use natural gas boiler backup when the heat pump boiler could not operate due to outdoor air conditions which are below its cutoff temperature. This measure helps to quantify the decarbonization as well as the energy savings potential from the replacement. The measure resulted higher savings in natural gas consumption compared to the increase in electricity consumption, with a ratio of 3. The total natural gas energy consumption was reduced by 41%, whereas the total electricity consumption was increased by 5.3%.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Description of the Gas Sampling and Circulation System for the LYNM PE1-A Experiment

A series of multiphysics experiments, referred to as Physics Experiment 1 (PE1) is underway at the U.S. Nevada National Security Site. The PE1 series includes detonations of three underground chemical explosions. As the name implies, there are a number of experiments investigating the signals generated by the explosion. The experiment series objectives are outlined in a report from Lawrence Livermore National Laboratory.1 One of the experiments is a gas migration experiment. Gas tracers were imbedded in the explosives and gas sampling boreholes were installed in the formation in the test bed. Connected to the monitoring points is a circulation system that moves gas to a central measurement location. This report does not describe the gas analysis or collection systems, but rather the circulation system that provides the gas for measurement. Here, we have combined four project documents into a single report that describes the design, build, installation, testing, and operation of the gas sampling network.

42 ENGINEERING↗

Radiolytic Gas Generation and Pressure Buildup in a Closed System Containing Mo-99 Solution

This study measured radiolytic gas generation and pressure buildup in a sealed stainless-steel system containing alkaline Mo-99 solution with added sodium nitrate as a hydrogen suppressant. In each of two experiments, approximately 200 Ci of Mo-99 solution was transferred into a closed experimental vessel inside a hot cell, isolated, and monitored for pressure rise caused by gas generation during radioactive decay. After pressure buildup, headspace gas samples were collected and analyzed by mass spectrometry to determine hydrogen and oxygen concentrations. The purpose was to quantify the magnitude of pressure buildup in a closed system and to characterize the gas composition produced by radiolysis of the Mo-99 target solution under representative handling and storage conditions. The two experiments used similar total Mo-99 activity but differed in solution volume, headspace volume, and leak integrity. In the first experiment, 197.5 Ci of Mo-99 in 16.92 mL of solution was loaded into a vessel with a 31.1-mL headspace; a small leak was later identified, and the measured peak pressure of 46 psig was extrapolated to about 70 psig in the absence of leakage. The headspace gas from this experiment contained about 21.4% H2 and 63.4% O2, but the composition was influenced by preferential hydrogen loss through the leak. In the second experiment, 193 Ci of Mo-99 in 5.41 mL of solution with 0.46 g NaNO3 was loaded into a vessel with a larger 42.61 mL headspace, and no detectable leak was observed. This experiment reached a peak pressure of 38 psig, and the measured gas composition was approximately 28.2% H2 and 51.5% O2. Because the second experiment was leak-free, it is considered the more reliable indicator of the true pressure buildup and intrinsic radiolytic gas composition of the Mo-99 solution.

Chemerisov, Sergey D.↗

Green spherules from Apollo 15 - Inferences about their origin from inert gas measurements.

Green spherules from the 'clod' 15426 and from fines 15421 contain about 100 times less trapped inert gases than normal bulk fines from Apollo 15. These spherules have apparently never been directly exposed to the solar wind. Spherules from other fines contain about 10 times more trapped gas than those from the 'clod.' The gas in the former is surface correlated. However, spherules from fines 15401 are exceptionally gas-poor. The trapped gases can be of solar-wind origin, but this origin requires a two-stage model for the spherules from the clods. Another possibility is that the gases were absorbed from an ambient gas phase. The trapped gases may also be assumed to represent primordial lunar gas. The composition of this gas is then similar to the 'solar' or 'unfractionated' component of gas-rich meteorites, but unlike that in most of the carbonaceous chondrites.

Lakatos, S.↗

Purging of a multilayer insulation with dacron tuft spacer by gas diffusion

The time and purge gas usage required to purge a multilayer insulation (MLI) panel with gaseous helium by means of gas diffusion to obtain a condensable gas (nitrogen) concentration of less than 1 percent within the panel are stipulated. Two different, flat, rectangular MLI panels, one incorporating a butt joint, were constructed of of 11 double-aluminized Mylar (DAM) radiation shields separated by Dacron tuft spacers. The DAM/Dacron tuft concept is known commercially as Superfloc. The nitrogen gas concentration as a function of time within the MLI panel could be adequately predicted by using a simple, one dimensional gas diffusion model in which the boundary conditions at the edge of the MLI panel were time dependent. The time and purge gas usage required to achieve 1 percent nitrogen gas concentration within the MLI panel varied from 208 to 86 minutes and 34.1 to 56.5 MLI panel purge volumes, respectively, for gaseous helium purge rates from 10 to 40 MLI panel volumes per hour.

Sumner, I. E.↗

Optically selective, acoustically resonant gas detecting transducer

A gas analyzer is disclosed which responds to the resonant absorption or emission spectrum of a specific gas by producing an acoustic resonance in a chamber containing a sample of that gas, and which measures the amount of that emission or absorption by measuring the strength of that acoustic resonance, e.g., the maximum periodic pressure, velocity or density achieved. In the preferred embodiment, a light beam is modulated periodically at the acoustical resonance frequency of a closed chamber which contains an optically dense sample of the gas of interest. Periodic heating of the absorbing gas by the light beam causes a cyclic expansion, movement, and pressure within the gas. An amplitude is reached where the increased losses were the cyclic radiation energy received. A transducing system is inclined for converting the pressure variations of the resonant gas into electronic readout signals.

Dimeff, J.↗