Search NASA⌕ Search

SEARCH · Search NASA

Results for “Clathrate”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Discovery of Ternary Antimonides A–Al–Sb (A = Rb or Cs) with Desired Structural Motifs Guided by Machine Learning

Specific structural motifs in inorganic solids are often related to their targeted physical properties. For many classes of solids, such as Zintl phases and polar intermetallics, the crystal structures are diverse and not easy to predict. Various antimonides that are potential thermoelectric materials were proposed to be synthesizable on the basis of their estimated formation energies. Their structures were broadly classified as clathrate, channel, layered, or network through a machine learning model trained on existing ternary phases and features based on elemental properties using the sure independence screening and sparsifying operator algorithm. Through experimental validation, three new ternary antimonides were synthesized and confirmed to form layered structures: tetragonal RbAlSb 2 and CsAlSb 2 , which are isopointal but not isotypic to LiBSi 2 ; and monoclinic Rb 2 Al 2 Sb 3 , which adopts the Na 2 Al 2 Sb 3 -type structure. Finally, reinvestigation of the related compound Cs 2 In 2 Sb 3 revealed a low thermal conductivity and p-type semiconducting behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

X-ray-diffraction and electrical-transport imaging of superconducting superhydride (La,Y)H 10

Understanding how microscopic structural domains govern macroscopic electronic properties is central to advancing hydride superconductors, yet such correlations remain poorly resolved under pressure. We report the synthesis and characterization of (La 0.9 Y 0.1 )H 10 superhydrides exhibiting coexisting cubic $Fm\bar{3}m$ and $P6_3/mmc$ hexagonal clathrate phases observed over the pressure range from 168 GPa down to 136 GPa. Using synchrotron-based X-ray diffraction imaging at the upgraded Advanced Photon Source, we spatially resolved μm-scale distributions of these phases, revealing structural inhomogeneity across the sample. Four-probe resistance measurements confirmed superconductivity with two distinct transitions: an onset at 244 K associated with the cubic phase and a second near 220 K linked to the hexagonal phase. Notably, resistance profiles collected from multiple current and voltage permutations showed variations in transition width and onset temperature that correlated with the spatial phase distribution. These findings demonstrate a direct connection between local structural domains and superconducting behavior.

Materials science↗
DOE OSTI2024

Effective optimization of atomic decoration in giant and superstructurally ordered crystals with machine learning

Crystals with complicated geometry are often observed with mixed chemical occupancy among Wyckoff sites, presenting a unique challenge for accurate atomic modeling. Similar systems possessing exact occupancy on all the sites can exhibit superstructural ordering, dramatically inflating the unit cell size. In this work, a crystal graph convolutional neural network (CGCNN) is used to predict optimal atomic decorations on fixed crystalline geometries. This is achieved with a site permutation search (SPS) optimization algorithm based on Monte Carlo moves combined with simulated annealing and basin-hopping techniques. Our approach relies on the evidence that, for a given chemical composition, a CGCNN estimates the correct energetic ordering of different atomic decorations, as predicted by electronic structure calculations. This provides a suitable energy landscape that can be optimized according to site occupation, allowing the prediction of chemical decoration in crystals exhibiting mixed or disordered occupancy, or superstructural ordering. Verification of the procedure is carried out on several known compounds, including the superstructurally ordered clathrate compound Rb8Ga27Sb16 and vacancy-ordered perovskite Cs2SnI6, neither of which was previously seen during the neural network training. In addition, the critical temperature of an order–disorder phase transition in solid solution CuZn is probed with our SPS routines by sampling site configuration trajectories in the canonical ensemble. This strategy provides an accurate method for determining favorable decoration in complex crystals and analyzing site occupation at unprecedented speed and scale.

Chemistry↗
DOE OSTI2024

Solvent organization in the ultrahigh-resolution crystal structure of crambin at room temperature

Ultrahigh-resolution structures provide unprecedented details about protein dynamics, hydrogen bonding and solvent networks. The reported 0.70 Å, room-temperature crystal structure of crambin is the highest-resolution ambient-temperature structure of a protein achieved to date. Sufficient data were collected to enable unrestrained refinement of the protein and associated solvent networks using SHELXL . Dynamic solvent networks resulting from alternative side-chain conformations and shifts in water positions are revealed, demonstrating that polypeptide flexibility and formation of clathrate-type structures at hydrophobic surfaces are the key features endowing crambin crystals with extraordinary diffraction power.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Gas Hydrate Film Growth in Microfluidic Channels for Carbon Dioxide Capture and Sequestration Applications

Gas or clathrate hydrates are a solid, crystalline compound composed of water and guest molecules that typically form at high pressure and low temperature conditions. Carbon dioxide (CO2) hydrates may be involved in several carbon dioxide capture and sequestration (CCS) applications, including CO2 pipeline transportation and CO2 offshore sequestration. Within these applications, the formation mechanism and kinetics must be well understood to manage the CCS processes, either by preventing or promoting hydrate formation. In this work, a high-pressure glass microfluidic reactor is used in tandem with visual microscopy and in-situ Raman spectroscopy to study both the morphological and kinetic behavior of gas hydrate crystals. Subcooling, pressure, and CO2 flow rate are investigated for their impact on the thickening behavior of pure CO2 hydrates, with flow rate being the only parameter to have a significant effect. Visual and Raman spectroscopy evidence show that both a dense hydrate layer and a porous hydrate layer form, and the latter may provide a path for mass transfer to continue hydrate crystallization. A first principles mass transfer model is developed to describe CO2 hydrate crystal thickening at the interface between gas and water. The impacts of gas impurities and channel wettability are also studied. This method is further applied to investigate the conversion of methane hydrate to CO2 hydrate for combined energy recovery and methane hydrate formation. The authors acknowledge the US Department of Energy Basic Energy Science award # DE-SC0022162.

Wadsworth, Lindsey [Colorado School of Mines, Gold↗
DOE OSTI2026

Towards libraries of different ultrasmall amorphous silica cage topologies

Cage topology controlled at the nanometer length scale is expected to enable original functionalities, e.g., in catalysis and therapeutics. Cages are fundamental structural motifs of clathrates and their topological duals, Frank-Kasper phases, and are constituents of mesoporous silica frameworks. However, with one exception, they have not been synthesized as discrete particles. By varying reactant ratios of surfactant, oil, and silane, we report the discovery of 5(12)6(2) and 5(12)6(8) amorphous silica polyhedra, each coexisting with the previously identified 5(12) cage, using combined cryo-transmission electron microscopy (cryo-TEM) and single-particle reconstruction (SPR). Notably, the 5(12)6(8) polyhedron represents a topology not previously observed in mesoporous silica frameworks. Control over structural features is demonstrated, and insights into cage formation mechanisms are provided. Structural outcomes are summarized in a ternary morphology diagram alongside prior results, bridging serendipitous discovery and intentional design of silica cages displaying a level of control over silica polymerization rivaling nature.

Jang, Dong June [Department of Materials Science a↗
NASA NTRS1972

Cometary Nuclei: Models

Arguments for the existence of some kind of icy-conglomerate cometary nucleus are put forward, and the role of clathrates in the condensation of comets from the solar nebula is discussed. The division of cosmic materials into three types is described, and it is suggested that whereas Jupiter, and to a large extent Saturn, condensed directly from gas and the terrestrial planets and asteroids collected from planetesimals of earthy material, the comets were formed as snow balls in the vicinity of Uranus and Neptune, with these two planets themselves representing accumulations of comets. The evidence for the existence of a comet belt beyond Neptune is considered, and it is concluded that at 50 AU from the sun the mass of such a belt cannot be more than that of the Earth. Finally, some of the problems associated with the mission to periodic Comet d'Arrest are discussed, in particular those concerned with the detectability of the nucleus and the hazards of a close encounter.

Whipple, F. L.↗
NASA NTRS1972

Nature and Origin of Cometary Heads

In cometary spectra the three major constituents seem to be OH, H, and O. Their common precursor is likely to be water, whose rates of evaporation and dissociation have so far not led to a major discrepancy with the observations. This type of explanation, however, has not led to a positive identification of other parent molecules. With the known solar intensities, all the molecules that have been suggested, as NH3, CH4, etc, would lead to lifetimes one-to-two orders of magnitude larger than needed by the coma observations. An alternate hypothesis is that the precursors are not molecules, but icy particles stripped from the nucleus by the evaporating gases. By evaporating within an icy halo, the grains would liberate either parent molecules with very short lifetimes or some of the radicals themselves. Recent laboratory work suggests that the grains could be made of clathrate hydrates of gases or of radicals. The observations appear to indicate the presence of icy grains within the inner coma.

Delsemme, A. H.↗
NASA NTRS1972

Further Comments on Photochemistry

The formation processes for C3 or C2 in comets are discussed along with the possibility of trapping the radical inside the clathrates.

Jackson, W. M.↗
NASA NTRS1973

Liquid carbon dioxide and the Martian polar laminae

One of the most important findings of the Mariner 9 mission was the existence of a set of apparent stacked layers in both the north and south polar regions of Mars. The total thickness of the laminated terrain is approximately several kilometers. Because the Martian atmosphere is composed largely of CO2 and because the frost point of CO2 is known to be reached in both polar regions, it has been assumed that the volatiles in the bright laminae are in appreciable part condensed CO2, although condensed H2O, and a CO2-H2O clathrate are also possible. As long as the ratio of CO2 to H2O is large, the physical properties will be dominated by the CO2.

Sagan, C.↗
NASA NTRS1973

Solubilities of noble gases in magnetite - Implications for planetary gases in meteorites.

Solubilities of noble gases in magnetite were determined by growing magnetite in a noble-gas atmosphere between 450 and 700 K. Henry's law is obeyed at pressures up to .01 atm for He, Ne, Ar and up to .00001 atm for Kr, Xe, with the following distribution coefficients at 500 K: He 0.042, Ne 0.016, Ar 3.6, Kr 1.3, Xe 0.88, some 100 to 100,000 times higher than previous determinations on silicate and fluoride melts. Apparent heats of solution are in sharp contrast with earlier determinations on melts which were small and positive, but are comparable to the values for clathrates. Presumably the gases are held in anion vacancies.

Lancet, M. S.↗
NASA NTRS1974

Mars - The case against permanent CO2 frost caps

Leighton and Murray (1966) have argued that there is a polar reservoir of solid CO2 on Mars that lasts throughout the year and whose vapor pressure determines the mean partial pressure of CO2 in the atmosphere. This model is discussed in the light of recent data, and several difficulties emerge. First, such a system might be unstable, owing to the tendency of poleward heat transport to increase with atmospheric pressure. Second, the annual retreat of the CO2 frost cover would be slower according to the model than that observed. Moreover, the observations seem to indicate that the residual polar cap that lasts throughout the year is composed of water ice rather than CO2. Finally, observations of water vapor in the atmosphere appear to be inconsistent with a permanent CO2 cold trap in continuous existence for many years. These difficulties hold also for a CO2 reservoir buried by water ice and for a hydrated CO2 clathrate.

Ingersoll, A. P.↗
NASA NTRS1976

Ice in space: An experimental and theoretical investigation

The thermodynamics of water ice formation was experimentally investigated under a wide variety of conditions, including those of outer space. This information, and in particular, the lifetime of ice particles as a function of solar distance is an absolute requirement for proper interpretation of photometric profiles of comets. The sublimation of ice particles in a nonequilibrium situation was studied. An oscillating fiber microbalance was used to measure the sublimation rate of water droplets (which were suspended on a long quartz fiber which was oscillating in a vacuum chamber). The influence of particle size, surface temperature, and the index refraction from simulated solar radiation were studied in relation to ice formation. Also examined was the influence of impurities (clathrates) on ice formation. Windows in the vacuum chamber allowed the ice particles to be exposed to a 1 kilowatt xenon arc lamp which was used to simulate solar radiation. Ice is proposed as a possible energy source for comets, as amorphous water ice and ammonia in low temperature and pressure environments demonstrated a clear energy release upon warming. Motion pictures of ice formation were taken and photographs are shown.

Patashnick, H.↗
NASA NTRS1976

Physical processes in Comet Kohoutek

Observational results are brought together to establish the mass loss of Comet Kohoutek (1973 XII) in H2O, solid particles, and other molecules. The production rate of molecules is seen to have flattened prior to peaking near perihelion passage, and then fell below the rate for the incoming branch of the orbit. The total mass loss was about 10 to the 14th power gm. All abundances are consistent with a clathrate-dominant form of water. Comparison of the sizes of the nucleus as calculated from photometry and the rate of water loss requires that either an unrealistically high albedo be assumed or that only a portion of the nucleus was covered by water, in contrast with previous expectations for a new and probable first-passage comet. Moreover, if the preperihelion estimates of the nuclear brightness are rejected as being contaminated, the resulting values indicate an ice-covered nucleus with a radius of 2.1 km.

Odell, C. R.↗
NASA NTRS1977

Saturn's rings - A new survey

Observations of radar returns from Saturn's rings, together with radio interferometry of their absorption of radiation from the disk, combine to require an effective radius of ring particles of about 6 cm or larger. It is suggested that the ring particles may also include, in addition to the known ice constituent, a mixture of the clathrated hydrate of methane and ammonia hydrate. A two-density model for ring particles is possible in which a matrix of low density contains many nodules of higher-density ice particles; in this case, radii nearly as large as the observed ring thickness would be possible. Improved resolution in radio observations at 21 cm or, if necessary, at longer wavelengths for narrow ring openings is perhaps the most useful method for determining upper limits on the particle size.

Cook, A. F.↗
NASA NTRS1978

On the monochromatic brightness variations of comets

The nonsteady development of the multispecies atmosphere of a long-period comet approaching the sun is modeled, and the associated monochromatic brightness variations are discussed in terms of the varying abundances of the atmospheric species. A simple homogeneous clathrate structure, 85% of which is H2O, provides the representation for the cometary nucleus. Monochromatic brightness variations of the emission bands due to OH, CN and C2 are found to follow the law proposed by Levin (1943) for small heliocentric distance where a quasi-steady approximation is valid. However, the large time-scales of residence for emitting species leads to a breakdown of Levin's law at large heliocentric distances.

Mendis, D. A.↗
NASA NTRS1979

Seasonal recession of Mars' south polar cap as seen by Viking

The spring-summer retreat of the south polar cap of Mars is portrayed in photomosaics obtained by Viking Orbiter 2 during 1977. Comparisons of these data to Mariner 9 photos and to the record of telescopic observations attest that the polar retreat viewed by Viking was significantly slower than those previously reported. A global dust storm which occurred at an unusually early season may have effected this retarded recession by introducing dust into the atmosphere of Mars which modified the polar energy balance through scattering of incident radiation. The composition of the south residual cap cannot be unambiguously determined at this time; however, some data suggest that CO2 or clathrate survived the entire summer viewed by Viking.

James, P. B.↗
NASA NTRS1979

Vaporization of comet nuclei - Light curves and life times

The effects of vaporization from the nucleus of a comet are examined and it is shown that a latitude dependence of vaporization can explain the asymmetries in cometary light curves. An attempt is made to explain the observed variation in molecular production rates with heliocentric distance when employing CO2 and clathrate hydrate ice as cometary nuclei substances. The energy balance equation and the vapor pressure equations of water and CO2 are used in calculating the vaporization from a surface. Calculations were carried out from both dry-ice and water-ice nuclei, using a variety of different effective visual albedos, but primarily for a thermal infrared of 0 (emission). Attention is given to cometary lifetimes and light curves and it was determined that the asymmetry in light curves occurs (occasionally) as a 'seasonal' effect due to a variation in the angle between the comet's rotation axis and the sun-comet line.

Cowan, J. J.↗