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At least 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Confinement-Driven Heterogeneous Benzene Crystallization in Silica Nanopores

Nanoconfinement alters the thermodynamics, dynamics, and kinetics of fluids hosted in nanoscale solid nanopores to an extent that depends on the characteristics of the confining space and the chemistry of the confined fluids. Confinement-induced alterations in the phase behavior of confined energetic fluids under high pressure or low temperature are highly relevant to subsurface and subsea phenomena such as fluid flow in porous media, hydrate formation and dissociation, and gas storage capacity. Although extensive efforts have been directed toward understanding the phase behavior of confined fluids, the role of solid-liquid interfaces in the phase transitions of organic liquids has not been resolved yet. Here, we explore the onset and growth of benzene crystallization confined in 6 nm sized SBA-15 silica nanopores in the temperature range 300-200 K using in situ extended range small-angle and wide-angle X-ray scattering (SAXS/WAXS) measurements and atomistic classical molecular dynamics (MD) simulations. The crystallization onset of confined benzene depresses to 265 K compared to the freezing point of bulk benzene ( ~278 K), followed by the continuous growth of the emerged crystals in the pore space with complete crystallization at 200 K. The orientation of the emerged benzene crystals is dominated by parallel (π-π stacking) and perpendicular (T-shape stacking) orientations along the cylindrical pore radius and pore length, respectively. The onset of benzene crystals occurs heterogeneously on the pore surface and grows continuously toward the pore center. Further, confined benzene undergoes a dynamical crossover from fragile to strong dynamics behavior, inferred from the rotational and translational diffusion. The insights provided by this study have significant implications for the phase transitions of confined organic liquids that are relevant to a wide range of applications in the biological, geological, environmental, and chemical fields.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1991

Low-pressure clathrate-hydrate formation in amorphous astrophysical ice analogs

In modeling cometary ice, the properties of clathrate hydrates were used to explain anomalous gas release at large radial distances from the Sun, and the retention of particular gas inventories at elevated temperatures. Clathrates may also have been important early in solar system history. However, there has never been a reasonable mechanism proposed for clathrate formation under the low pressures typical of these environments. For the first time, it was shown that clathrate hydrates can be formed by warming and annealing amorphous mixed molecular ices at low pressures. The complex microstructures which occur as a result of clathrate formation from the solid state may provide an explanation for a variety of unexplained phenomena. The vacuum and imaging systems of an Hitachi H-500H Analytical Electron Microscope was modified to study mixed molecular ices at temperatures between 12 and 373 K. The resulting ices are characterized by low-electron dose Transmission Electron Microscopy (TEM) and Selected Area Electron Diffraction (SAED). The implications of these results for the mechanical and gas release properties of comets are discussed. Laboratory IR data from similar ices are presented which suggest the possibility of remotely observing and identifying clathrates in astrophysical objects.

Blake, D. F.↗
DOE OSTI2023

Early age hydration behavior of portland cement-based binders incorporating fly ash contaminated with flue gas desulfurization products

Fly ash co-mingled with flue gas desulfurization (FGD) products are currently discarded as off-specification materials based on their high SO3 content. However, previous studies have shown that performance of these fly ashes varies significantly based on FGD product type and as such they may be viable for use in low-CO2 concrete as supplementary cementitious materials (SCMs). In this study, fly ashes with three different types of FGD products including calcium sulfite hemihydrate, calcium sulfate (with some unreacted lime), and sodium sulfate (with some unreacted sodium carbonate) were evaluated. The early age hydration behavior in blended cementitious systems at 20% cement replacement level was studied using Vicat setting time tests, isothermal calorimetry, in-situ quantitative X-ray diffraction, and pore solution analysis. The cause of the setting time retardation and flash setting observed in fly ashes with calcium sulfite hemihydrate and sodium carbonate, respectively, were identified and suitable beneficiation options were suggested for the valorized use of these materials in low-CO 2 concrete.

36 MATERIALS SCIENCE↗
NASA NTRS1988

Trapping of gas mixtures by amorphous water ice

Our studies on gas trapping in amorphous water ice at 24-100 K were extended, by using mixtures of CH4, CO, N2, and Ar, rather than single gases. In 1:1 gas:(water vapor) mixtures, the competition among these gases on the available sites in the ice showed that the trapping capacity for the various gases is determined not only by the structure and dynamics of the ice, but is also influenced by the gas itself. Whereas at 24-35 K all four gases are trapped in the ice indiscriminantly, at 50-75 K there is a clear enhancement, in the order of CH4 > CO > N2 > or approximately Ar. This order is influenced by the gas-water interaction energy, the size of the trapped gas atom or molecule, the type of clathrate-hydrate formed (I or II) and, possibly, other factors. It seems that the gas can be trapped in the amorphous ice in several different locations, each being affected in a different way by the deposition temperature and gas composition. Once a gas atom or molecule is trapped in a specific location, it is predestined to emerge in one of eight different temperature ranges, which are associated with changes in the ice. The experimentally observed enhancements, together with the findings on the gas composition of comet Halley, might enable an estimation of the gas composition in the region of comet formation.

NASA Discipline Number 52-10↗
NASA NTRS1986

Non-solar noble gas abundances in the atmosphere of Jupiter

The thermodynamic stability of clathrate hydrate is calculated to predict the formation conditions corresponding to a range of solar system parameters. The calculations were performed using the statistical mechanical theory developed by van der Waals and Platteeuw (1959) and existing experimental data concerning clathrate hydrate and its components. Dissociation pressures and partition functions (Langmuir constants) are predicted at low pressure for CO clathrate (hydrate) using the properties of chemicals similar to CO. It is argued that nonsolar but well constrained noble gas abundances may be measurable by the Galileo spacecraft in the Jovian atmosphere if the observed carbon enhancement is due to bombardment of the atmosphere by clathrate-bearing planetesimals sometime after planetary formation. The noble gas abundances of the Jovian satellite Titan are predicted, assuming that most of the methane in Titan is accreted as clathrate. It is suggested that under thermodynamically appropriate conditions, complete clathration of water ice could have occurred in high-pressure nebulas around giant planets, but probably not in the outer solar nebula. The stability of clathrate in other pressure ranges is also discussed.

Lunine, Jonathan I.↗
NASA NTRS1997

A blast of gas in the latest Paleocene: simulating first-order effects of massive dissociation of oceanic methane hydrate

Carbonate and organic matter deposited during the latest Paleocene thermal maximum is characterized by a remarkable -2.5% excursion in delta 13C that occurred over approximately 10(4) yr and returned to near initial values in an exponential pattern over approximately 2 x 10(5) yr. It has been hypothesized that this excursion signifies transfer of 1.4 to 2.8 x 10(18) g of CH4 from oceanic hydrates to the combined ocean-atmosphere inorganic carbon reservoir. A scenario with 1.12 x 10(18) g of CH4 is numerically simulated here within the framework of the present-day global carbon cycle to test the plausibility of the hypothesis. We find that (1) the delta 13C of the deep ocean, shallow ocean, and atmosphere decreases by -2.3% over 10(4) yr and returns to initial values in an exponential pattern over approximately 2 x 10(5) yr; (2) the depth of the lysocline shoals by up to 400 m over 10(4) yr, and this rise is most pronounced in one ocean region; and (3) global surface temperature increases by approximately 2 degrees C over 10(4) yr and returns to initial values over approximately 2 x 10(6) yr. The first effect is quantitatively consistent with the geologic record; the latter two effects are qualitatively consistent with observations. Thus, significant CH4 release from oceanic hydrates is a plausible explanation for observed carbon cycle perturbations during the thermal maximum. This conclusion is of broad interest because the flux of CH4 invoked during the maximum is of similar magnitude to that released to the atmosphere from present-day anthropogenic CH4 sources.

Non-NASA Center↗
DOE OSTI2021

Methane Hydrate Formation and Evolution During Sedimentation

We explored methane hydrate formation with sedimentation with a newly developed one-dimensional, multiphase flow, multicomponent transport numerical model. Our model couples methane hydrate formation from in situ microbial methane generation within the hydrate stability zone (HSZ), methane recycling, and microbial methane generation below the base of the hydrate stability zone (BHSZ). Both recycled methane and deeply generated methane are transported into the HSZ by buoyancy-driven free gas flow. Free gas flows through the HSZ by both the processes of capillary-dependent pore fillings and by salt exclusion during hydrate formation, with the former being the dominant mechanism. We quantitively illustrated the formation of enriched hydrate in muddy sediments above, and interconnected free gas below, the BHSZ, which are common features along the world's continental margin. In addition, we showed two ways to form concentrated methane hydrate above the BHSZ. The first mechanism is local free gas flow during methane recycling. This happens at sites with sufficient methane generation above the BHSZ. The second mechanism is deep microbial methane generation which is transported into the HSZ by free gas flow. This mechanism plays a more important role at sites with high sedimentation rates. This study provides new insights into methane hydrate formation and distribution below the seafloor. It is important for understanding the carbon cycle and carbon storage below the seafloor and for resource evaluation and exploitation.

58 GEOSCIENCES↗
DOE OSTI2021

Milestone 1.2.9: Radiolytic Gas Generation Measurements from Helium Backfilled Samples of AA1100 and AA6061 Coupons

Nearly 18 metric tons of aluminum-clad spent nuclear fuel (ASNF) is safely managed by the U.S. Department of Energy (DOE). These assemblies are currently in interim storage, with the intention of extended storage (>50 years) until final disposal. Strategies for the continued safe storage of this material are under evaluation, of which a key criterion is the extent of molecular hydrogen gas (H2) formation from the radiolysis of hydrated (oxy)hydroxide aluminum corrosion layers arising from in-reactor and wet storage conditions. Radiation-induced H2 formation has the potential to compromise cladding and storage canister integrity, in addition to promoting the formation of unfavorable gaseous environments. Consequently, understanding this radiation-induced phenomenon is essential for the development of predictive modeling capabilities to support technical considerations and the identification of radiation related challenges for the extended storage of ASNF. Here, we report radiolytic H2 yields (G-values, G(H2)) from the gamma irradiation of ‘pristine’ and pre-corroded aluminum coupons in helium (He) environments as a function of alloy composition (AA1100 and AA6061), relative humidity, and absorbed gamma dose. Measured yields were lower than corresponding values reported for argon environments, a positive result for proposed extended dry storage strategies that would employ helium as a backfill gas. Interestingly, the presented G(H2)He values are comparable to those previously measured in nitrogen environments, suggesting a He mediated H2 inhibition process, attributed here to Penning ionization.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2022

Separation of CO 2 from Flue Gas and Potential for Geologic Sequestration

The objectives of this study were to review various methods reported in the literature for the separation and geologic sequestration of carbon dioxide and evaluate the potential of TVA fossil fuel-burning plant locations for onsite geologic sequestration of CO 2 from stack emissions. Several conventional and nonconventional technologies for the separation of CO 2 from flue gas, including absorption, adsorption, cryogenic distillation, membranes, hydrate formation and dissociation, and ammonia carbonation, have been reviewed in terms of separation mechanisms, flow diagrams, and costs. Most of the technologies that have been reviewed are still at the research and development stage. Critical information needed to assess and compare these technologies is still lacking. In addition, information on some of the technologies that have been tested at a pilot or industrial scale has not been fully disclosed in the open literature. Because of this lack of data, it is difficult to make a critical assessment of each of the separation technologies. Based on limited information, it was concluded that the most promising methods are membrane separation and the Mitsubishi process for chemical absorption. Both processes involve separating CO 2 at high temperature, minimizing the cost for cooling prior to separation. Physical and chemical geologic formations of CO 2 were also reviewed. It was concluded that due to the geologic time scale of CO 2 sequestration periods, relatively safe conditions, general proximity to CO 2 sources, and extensive knowledge of underground conditions, sequestration of CO 2 in underground aquifers and coal beds is a very promising method of mitigating greenhouse gas emissions. The cost is predicted to be relatively low and the suitable sites are numerous for this application, with many of these sites located close to the plants.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2021

Analysis of natural gas bubble in NETL High Pressure Water Tunnel (HPWT) experiment and its application to natural seeps

Conference Presentation at the 9th International Symposium on Environmental Hydraulics. Analysis of natural gas bubbles under deep-ocean conditions, including hydrate armoring. Compares numerical simulations using the Texas A&M Oil spill / outfall Calculator (TAMOC) to data observed in the NETL High Pressure Water Tunnel. Also, presents simulations of natural seep bubbles in the oceans off the coast of Oregon with comparison to acoustic observations of natural gas seep flares.

Kim, Byungjin↗
DOE OSTI2022

Kinetic Control of Angstrom-Scale Porosity in 2D Lattices for Direct Scalable Synthesis of Atomically Thin Proton Exchange Membranes

Angstrom-scale pores introduced into atomically thin 2D materials offer transformative advances for proton exchange membranes in several energy applications. Here, we show that facile kinetic control of scalable chemical vapor deposition (CVD) can allow for direct formation of angstrom-scale proton-selective pores in monolayer graphene with significant hindrance to even small, hydrated ions (K + diameter ~6.6 Å) and gas molecules (H 2 kinetic diameter ~2.9 Å). We demonstrate centimeter-scale Nafion|Graphene|Nafion membranes with proton conductance ~3.3–3.8 S cm –2 (graphene ~12.7–24.6 S cm –2 ) and H + /K + selectivity ~6.2–44.2 with liquid electrolytes. The same membranes show proton conductance ~4.6–4.8 S cm –2 (graphene ~39.9–57.5 S cm –2 ) and extremely low H 2 crossover ~1.7 × 10 –1 – 2.2 × 10 –1 mA cm –2 (~0.4 V, ~25 °C) with H 2 gas feed. We rationalize our findings via a resistance-based transport model and introduce a stacking approach that leverages combinatorial effects of interdefect distance and interlayer transport to allow for Nafion|Graphene|Graphene|Nafion membranes with H + /K + selectivity ~86.1 (at 1 M) and record low H 2 crossover current density ~2.5 × 10 –2 mA cm –2 , up to ~90% lower than state-of-the-art ionomer Nafion membranes ~2.7 × 10 –1 mA cm –2 under identical conditions, while still maintaining proton conductance ~4.2 S cm –2 (graphene stack ~20.8 S cm –2 ) comparable to that for Nafion of ~5.2 S cm –2 . Furthermore, our experimental insights enable functional atomically thin high flux proton exchange membranes with minimal crossover.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Simulation of axial tensile well deformation during reservoir compaction in offshore unconsolidated methane hydrate-bearing formation

Sand production encountered in the 2013 offshore field gas production tests at the Nankai Trough, Japan, could be attributed to well failure during reservoir compaction. In this study, well integrity under various reservoir compaction patterns for the Nankai Trough case is examined using a well-formation finite element model. Here, the modelling details include the inclusion of a cement sheath as well as the modelling of construction processes (such as cement shrinkage). Well elongation in the overburden layer becomes significant when the reservoir subsidence is localized near the wellbore under large depressurization. Results show that the maximum plastic deviatoric strain level in the cement could reach 0.7% when the maximum reservoir subsidence reaches 0.85 m and cement shrinkage is limited. When cement shrinkage rises to 0.75%, the maximum plastic deviatoric strain increases to 2.4% as the cement accumulates additional plastic strain during shrinkage due to its deformation being constrained by the casing. In order to prevent the cement from failure, it might be effective to hold the pressure drawdown at a low level (e.g., several MPa) until the hydrate dissociation front advances to a certain radius from the well (e.g., a couple of tens of metres).

58 GEOSCIENCES↗
DOE OSTI2022

How the Hydrophobic Interface between a Perfluorosulfonic Acid Polymer and Water Vapor Controls Membrane Hydration

Stable hydration in perfluorinated polyelectrolyte membranes such as Nafion is essential to maintain good ion conductivity and manage permeation, especially in vapor-fed devices where water content depends on relative humidity in a gas stream. Extensive studies in the literature have shown that Nafion hydration in water vapor is controlled by its interfacial transport resistance. Nafion forms a fluorine-rich layer at the polymer-gas interface, and it has been proposed that this layer blocks water transport due to its hydrophobicity. To develop a molecular-level description of the physics underlying transport resistance in this system, we have performed a computational reaction-diffusion kinetics study of water evaporation from Nafion. Two distinct models are examined, one mimicking the blocking function proposed in the literature and the other assuming that there is no blocking, treating instead water evaporation as a dynamic balance between uptake from the gas and desorption from the polymer surface. Simulation results are compared to time-dependent infrared data over a range of 100-0% relative humidity from the literature. Only the dynamic model successfully reproduces experimental observations. This indicates that the physical nature of interfacial transport resistance is not slow diffusion across an interfacial layer; rather, it is due to the competition between dehydration and rehydration. The simulation data provide details on the accompanying water distributions throughout the membrane and on interfacial kinetics, showing that they are characterized by strong fluctuations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Electron ionization of clusters containing the formamide molecule

Abstract Studies on electron interactions with formamide (FA) clusters promote scientific interest as a model system to understand phenomena relevant to astrophysical, prebiotic, and radiobiological processes. In this work, mass spectrometric detection of cationic species for both small bare and microhydrated formamide clusters was performed at an electron ionization of 70 eV. Furthermore, a comparative analysis of the cluster spectra with the literature-reported gas-phase spectra is presented and discussed, revealing different reaction channels affected by the cluster environment. This study is essential in developing our understanding of both low-energy electron phenomena in clusters that can bridge the complexity gap between gas and realistic systems and the effect of hydration on electron-induced processes.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
NASA NTRS2004

Permanent Sequestration of Emitted Gases in the Form of Clathrate Hydrates

Underground sequestration has been proposed as a novel method of permanent disposal of harmful gases emitted into the atmosphere as a result of human activity. The method was conceived primarily for disposal of carbon dioxide (CO2, greenhouse gas causing global warming), but could also be applied to CO, H2S, NOx, and chorofluorocarbons (CFCs, which are super greenhouse gases). The method is based on the fact that clathrate hydrates (e.g., CO2 6H2O) form naturally from the substances in question (e.g., CO2) and liquid water in the pores of sub-permafrost rocks at stabilizing pressures and temperatures. The proposed method would be volumetrically efficient: In the case of CO2, each volume of hydrate can contain as much as 184 volumes of gas. Temperature and pressure conditions that favor the formation of stable clathrate hydrates exist in depleted oil reservoirs that lie under permafrost. For example, CO2-6H2O forms naturally at a temperature of 0 C and pressure of 1.22 MPa. Using this measurement, it has been calculated that the minimum thickness of continuous permafrost needed to stabilize CO2 clathrate hydrate is only about 100 m, and the base of the permafrost is known to be considerably deeper at certain locations (e.g., about 600 m at Prudhoe Bay in Alaska). In this disposal method, the permafrost layers over the reservoirs would act as impermeable lids that would prevent dissociation of the clathrates and diffusion of the evolved gases up through pores.

Duxbury, N.↗
NASA NTRS2007

Methane Hydrates: More Than a Viable Aviation Fuel Feedstock Option

Demand for hydrocarbon fuels is steadily increasing, and greenhouse gas emissions continue to rise unabated with the energy demand. Alternate fuels will be coming on line to meet that demand. This report examines the recovering of methane from methane hydrates for fuel to meet this demand rather than permitting its natural release into the environment, which will be detrimental to the planet. Some background on the nature, vast sizes, and stability of sedimentary and permafrost formations of hydrates are discussed. A few examples of the severe problems associated with methane recovery from these hydrates are presented along with the potential impact on the environment and coastal waters. Future availability of methane from hydrates may become an attractive option for aviation fueling, and so future aircraft design associated with methane fueling is considered.

Hendricks, Robert C.↗
NASA NTRS2018

ISRU Soil Water Extraction: Thermal Challenges

Water extraction from regolith requires significant energy input; heating efficiency is key to system power balanceRegolith has low thermal conductivityRecuperated heat from either reacted regolith or other systems merits examination, but must be done at the system model level (not component level)Water capture system may require significant reduction in temperature of the water vapor (e.g. condenser) Unknown parameters for modeling include:Residence time for water releaseConvection/conduction coefficients (sweep gas and/or flowing soil)Heat of dehydration for Mars hydrates.

Kleinhenz, Julie↗
DOE OSTI2024

Comparison of volatiles evolving from selected highland and mare lunar regolith simulants during vacuum sintering

Volatiles evolving from JSC-1A, NU-LHT-4M and CSM-LHT-1G lunar regolith simulants during in vacuo thermal processing were analyzed using mass spectrometry as a function of temperature. Two high-fidelity simulants, JSC-1A (mare) and NU-LHT-4M (highland), were compared to a newly developed CSM-LHT-1G highland simulant, modified to closely match lunar geochemistry. Large autogenous gas loads were observed for all investigated materials. Mineralogical knowledge was used to identify and attribute individual volatile species to reacting, transforming, or decomposing constituents (hydrates, carbonates, sulfates, sulfides, clays, etc.) of the respective regolith simulant in the self-generated gas environment. Cumulative mass losses for individual simulant components as a function of temperature were quantified using mass spectrometry in conjunction with thermogravimetric analysis. Investigation of the four components of CSM-LHT-1G – anorthosite, basalt, augite, and glass – aided the attribution of volatile species to specific compounds and their respective sources. The results showed significant decomposition of non-lunar phases present in the man-made regolith simulants below the typical glass crystallization temperatures, which paves the way to devising methods for enhancing the fidelity of the simulants. Finally, high gas loads and corrosive gases (HF and HCl) were recognized as potential hazards, pertaining to the development of large testbed facilities.

42 ENGINEERING↗