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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.

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All sourcesNASA NTRSDOE OSTI
NASA NTRS1994

Hydrogen storage in Earth's mantle and core

Two different approaches to explaining how hydrogen might be stored in the mantle are illustrated by a number of papers published over the past 25-30 years, but there has been little attempt to provide objective comparisons of the two. One approach invokes the presence in the mantle of dense hydrous magnesium silicates (DHMS) stable at elevated pressures and temperatures. The other involves nominally anhydrous minerals (NAM) that contain hydrogen as a minor constituent on the ppm level. Experimental studies on DHMS indicate these phases may be stable to pressures and temperatures as high at 16 GPa and 1200 C. This temperature is lower than that indicated by a mantle geotherm at 16 GPa, but may be reasonable for a subducting slab. It is possible that other DHMS could be stable to even higher pressures, but little is known about maximum temperature limits. For NAM, small amounts of hydrogen (up to several hundred ppm) have been detected in olivine, orthopyroxene, clinopyroxene, and garnet recovered from xenoliths in kimberlites, eclogites, and alkali basalts; it has been demonstrated that synthetic wadsleyite and perovskite can accommodate significant amounts of hydrogen. A number of problems are associated with each possibility. For NAM originating in the mantle, one would like to assume that the hydrogen measured in samples recovered on Earth's surface was incorporated when the phase-crystallized at high temperatures and pressures, but it could have been introduced during transport to the surface. Major problems for the DHMS proponents are that none of these phases have been found as minerals and little is yet known about their stabilities in systems containing other cations such as Fe, Al, and Ca.

Prewitt, Charles T.↗
NASA NTRS2014

Experimental Constraints on a Vesta Magma Ocean

A magma ocean model was devised to relate eucrites (basalts) and diogenites (orthopyroxenites), which are found mixed together as clasts in a suite of polymict breccias known as howardites. The intimate association of eucritic and diogenitic clasts in howardites argues strongly that these three classes of achondritic meteorites all originated from the same planetoid. Reflectance spectral evidence (including that from the DAWN mission) has long suggested that Vesta is indeed the Eucrite Parent Body. Specifically, the magma ocean model was generated as follows: (i) the bulk Vesta composition was taken to be 0.3 CV chondrite + 0.7 L chondrite but using only 10% of the Na2O from this mixture; (ii) this composition is allowed to crystallize at 500 bar until approx. 80% of the system is solid olivine + low-Ca pyroxene; (iii) the remaining 20% liquid crystallizes at one bar from 1250C to 1110C, a temperature slightly above the eucrite solidus. All crystallization calculations were performed using MELTS. In this model, diogenites are produced by cocrystallization of olivine and pyroxene in the >1250C temperature regime, with Main Group eucrite liquids being generated in the 1300-1250C temperature interval. Low-Ca pyroxene reappears at 1210C in the one-bar calculations and fractionates the residual liquid to produce evolved eucrite compositions (Stannern Trend). We have attempted to experimentally reproduce the <1250C portion of the MELTS Vesta magma ocean. In the MELTS calculation, the change from 500 bar to one bar results in a shift of the olivine:low-Ca pyroxene boundary so that the 1250C liquid is now in the olivine field and, consequently, olivine should be the first-crystallizing phase, followed by low-Ca pyroxene at 1210C, and plagioclase at 1170C. Because at one bar the olivine:low-Ca pyroxene boundary is a peritectic, fractional crystallization of the 1210C liquid proceeds with only pyroxene crystallization until plagioclase appears. Thus, the predictions of the MELTS calculation are clear and straightforward.

Hoff, C.↗
NASA NTRS1985

Undercooling of molten silicon

Droplets of uncoated molten Si(0.4-0.8 mm diameter) have been undercooled 250 C. Ge droplets of similar size have been undercooled 280 C in a B2O3 flux. The observed nucleation onset temperatures of both Si and Ge droplets are at or below the predicted amorphous phase melting temperatures T(al). The solidified structures were polycrystalline. The nucleation frequency I, calculated from the Si data (20,000/cu cm s at 240 + or - 20 C undercooling), should be an upper limit of the homogeneous nucleation frequency of the crystal phase, since it has not been established that nucleation was homogeneous in these experiments. However, this limiting I for Si indicates that homogeneous nucleation of crystal would not become appreciable in laser pulsing experiments until the liquid Si is undercooled to well below T(al).

Devaud, G.↗
NASA NTRS2002

Stability of Pseudobrookite-Type Titanium Oxides

Orthorhombic, (Bbmm), (Al, Fe, Cr, Ti)(sub 2) TiO5-(Mg, Fe)Ti2O5 solid solutions (pseudobrookites, s.l.) are found either as an oxidation product of ilmenite and/or spinel or a primary crystallizing phase in igneous and metamorphic rocks on Earth (e.g., basalt flows, crustal and mantle xenoliths, hornfels), and basaltic rocks on the Moon. Moreover, orthorhombic oxides are often part of the crystalline matrix in glass/ceramics with useful applications, and play a major role in the industrial production of TiO2. To fully exploit the potential of these compounds as petrogenetic indicators and/or useful materials we need to quantitatively understand the factors controlling their properties and stability, and thus, to extrapolate beyond the calibrating experiments. For that purpose, we need to combine thermochemistry, phase equilibrium, and in situ P-V-T-cation disorder experimental data that presently either are incomplete or lacking. Perhaps, the most complete data set is that for MgTi2O5 (karrooite) which allows the calibration of models for the Gibbs free energy of the MgTi2O5 as a function of pressure, temperature, and the Mg2+-Ti4+ distribution between the two nonequivalent octahedral sites. Consequently, the effect of cation disorder on MgTi2O5 stability, and the phase relations among MgTi2O5, other titanium oxides, and silicate minerals can be examined. Calculated phase relations in the Mg-Ti-Si-O system and phase equilibrium experiments in Fe-bearing compositions suggest that pseudobrookite-type oxides may be a more common in rocks than previously realized. However, homogeneous and heterogeneous equilibria, and crystallization paths likely affect their stability. For example, isobaric increases in temperature favor disordering and thus entropy-stabilization, in contrast, isothermal increases in pressure have the opposite effect. Although, currently, the potential effect of composition to cation disorder cannot be fully explored, it appears that enrichment in trivalent cations probably enhances entropy-stabilization and thus may increase the stability of (Al, Fe, Cr, Ti)-rich pseudobrookites relative to that of (Mg, Fe)-rich ones. In addition, high-temperature, nearly isothermal, decompression paths of olivine+orthopyroxene+oxide assemblages may favor pseudobrookites (s.l.) over rutile and/or ilmenite, in contrast, cooling at low pressures seems to favor ilmenite and/or rutile. In the case of crustal and mantle xenoliths, the presence or absence of orthorhombic oxides is probably controlled by reactions with olivine, orthopyroxene, ilmenite, and rutile. In oceanic mantle xenoliths such reactions may also involve a TiO2-enriched but not SiO2-enriched melt/fluid, because pseudobrookites (s.l.) would react with the SiO2-enriched melt/fluid to form orthopyroxene and rutile. Parenthetically, experiments and model calculations in the Mg-Ti-Si-O system suggest that low degree partial melting of low-TiO2 bulk compositions may produce Ti-enriched liquids in equilibrium with olivine, orthopyroxen ad=nd MgTi2O5, rutile or ilmenite.

Xirouchakis, Dimistrios↗
NASA NTRS2014

The Lunar Magma Ocean: Sharpening the Focus on Process and Composition

The currently accepted model for the formation of the lunar anorthositic crust is by flotation from a crystallizing lunar magma ocean (LMO) shortly following lunar accretion. Anorthositic crust is globally distributed and old, whereas the mare basalts are younger and derived from a source region that has experienced plagioclase extraction. Several attempts at modelling such a crystallization sequence have been made [e.g. 1, 2], but our ever-increasing knowledge of the lunar samples and surface have raised as many questions as these models have answered. This abstract presents results from our ongoing ex-periments simulating LMO crystallization and address-ing a range of variables. We investigate two bulk com-positions, which span most of the range of suggested lunar bulk compositions, from the refractory element enriched Taylor Whole Moon (TWM) [3] to the more Earth-like Lunar Primitive Upper Mantle (LPUM) [4]. We also investigate two potential crystallization mod-els: Fully fractional, where crystallizing phases are separated from the magma as they form and sink (or float in the case of plagioclase) throughout magma ocean solidification; and a two-step process suggested by [1, 5] with an initial stage of equilibrium crystalliza-tion, where crystals remain entrained in the magma before the crystal burden increases viscosity enough that convection slows and the crystals settle, followed by fractional crystallization. Here we consider the frac-tional crystallization part of this process; the equilibri-um cumulates having been determined by [6].

Rapp, J. F.↗
NASA NTRSDate not supplied

Location, location: deciphering the significance of in-situ hydrogen analyses of Martian meteorite phases

Understanding how inner planets acquired their volatiles such as hydrogen (H) is fundamental to constrain models of solar system formation [e.g. 1]. One avenue of estimating the H content and isotopic characteristics of differentiated planets is to analyze the samples we have from them as meteorites. Ideally, the H content and isotopic characteristic of the mantle sources of these igneous rocks should give insight into the volatile origin of each planetary body. The mantle H signatures can be estimated from that of the parent melt, which in turn may be derived from that of the first crystallized phases. However, we will illustrate the processes that can modify the H content and D/H ratios of pyroxene, olivine and feldspar in selected Martian meteorites relative to those of their mantle sources, with two key protocols for SIMS analysis. The first key is to put each analysis in textural context ("location, location"). In particular, of prime importance is whether an analysis is done at the center or the edge of a mineral grain, close or far from a shock disturbed area, and in a mineral crystallized at the beginning or late in the differentiation sequence. Accompanying the H analyses done by SIMS with major and trace element data at the same analysis locations allows to constrain the history of crystallization, cooling, alteration and shock of the meteorite. For example, volcanic degassing can be evidenced by decreasing water contents and increasing D/H ratios from core to edge of nakhlite pyroxenes [2]. Traverses of H analyses in pyroxene and maskelynite in shergottite LAR 06319 provide examples of H contents and D/H ratios modified during degassing following shock [3]. The second key is to assess if the area analyzed by SIMS has shock generated damage of the mineral structure, as will be shown in pyroxene and olivine from shergottite RBT 04262. Olivine in shergottites have too high water contents to be explained with an igneous origin and their D/H ratios are more consistent with terrestrial alteration, as observed before [4]. A review of all these processes shows how careful one has to be prior to using H measurements in meteorites to infer the origin and amount of water in differentiated planetary interiors.

A.H. Peslier↗
NASA NTRS1982

Crystal nucleation in Pd-Si alloys

A study of the crystal phase nucleation in undercooled droplets of Pd-Si alloys with composition near the Pd(84.5)Si(15.5) eutectic composition is reported. Molten droplets are released at the top of a drop tube and solidify (to either a crystalline or glassy state) during descent. This provides a containerless (and nearly gravity free) environment so that nucleation due to container walls or vibrations is eliminated. It is found that crystallization, due to homogeneous nucleation, is bypassed in droplets of 1 mm diameter when cooled at 760 K/sec. From this an upper limit of the homogeneous nucleation rate is estimated. Results are compared with a previously published study of nucleation in 0.06 mm to 0.33 mm diameter droplets, which indicated that nucleation results from heterogeneous surface nucleation and that the number of these nuclei is dependent on the atmosphere in the drop tube.

Drehman, A. J.↗
NASA NTRS2017

Volatile Concentrations and H-Isotope Composition of Unequilibrated Eucrites

Eucrites are among the oldest and best studied asteroidal basalts (1). They represent magmatism that occurred on their parent asteroid, likely 4-Vesta, starting at ~ 4563 Ma and continuing for approx. 30 Myr. Two hypotheses are debated for the genesis of eucrites, a magma ocean model (2), and a mantle partial melting model. In general, volatiles (H, C, F, Cl) have been ignored for eucrites and 4-Vesta, but solubility of wt% levels of H2O are possible at Vestan interior PT conditions. Targeted measurements on samples could aid our understanding considerably. Recent studies have found evidence of volatile elements in eucrites, but quantifying the abundance of volatiles remains problematic (6). Volatile elements have a disproportionately large effect on melt properties and phase stability, relative to their low abundance. The source of volatile elements can be elucidated by examining the hydrogen isotope ratio (D/H), as different H reservoirs have drastically different H isotope compositions. Recent studies of apatite in eucrites have shown that the D/H of 4-Vesta matches that of Earth and carbonaceous chondrites, however, the D/H of apatites may not represent the D/H of a primitive 4-Vesta melt due to the possibility of degassing prior to the crystallization of apatite. Therefore, the D/H of early crystallizing phases must be measured to determine if the D/H of 4-Vesta is equal to that of the Earth and carbonaceous chondrites.

Sarafian, Adam R.↗
NASA NTRS2021

Nanostructure and compositional segregation of soft magnetic FeNi-based nanocomposites with multiple nanocrystalline phases

Soft magnetic metal amorphous nanocomposite alloys are produced through rapid solidification and thermal annealing yielding nanocrystals embedded within an amorphous precursor. Similar free energies in Co-rich and FeNi-based alloy systems result in multiple nanocrystalline phases being formed during devitrification. Studies of multi-phase crystallization processes have been reported for Co-rich alloys but relatively few have investigated FeNi-based systems. A detailed characterization of compositional partitioning and microstructure of an optimally annealed FeNi-based MANC (Fe70Ni30)80Nb4Si2B14 alloy is presented through complementary high-resolution transmission electron microscopy (HRTEM) and atom probe tomography (APT). HRTEM demonstrates orientation relationships between FCC and BCC nanocrystals, suggesting heterogeneous nucleation of nanocrystals in the amorphous matrix or a cooperative mechanism of nucleation between BCC and FCC nanocrystallites. APT results show evidence for (i) the segregation of Fe and Ni between nanocrystals of different phases, (ii) B partitioning to the amorphous phase, and (iii) an Nb-enriched shell surrounding nanocrystals.

soft magnetic materials↗
NASA NTRSDate not supplied

Single-Scattering Properties of Melting Precipitation for GPM Passive Microwave and Radar Remote Sensing Applications

Over the past two decades, detailed computational simulations of the intricate three dimensional structures of ice-phase crystals and aggregates of those crystals have been developed. The microwave single-scattering properties of these simulated ice particles have been computed and used to improve quantitative estimates of snow rates and to better deRne the vertical structure of snow water contents in deep convective systems, as derived from satellite-borne passive microwave and/or radar remote sensing measurements. The same icephase particles have more recently been used as the starting point for simulations of melting precipitation using computational melting methods. In the current study, a heuristic melting method, as well as a physically-based melting procedure based on smoothed-particle hydrodynamics, are applied to ice particle models to describe the full evolution of the particles from dry snow to liquid drops. The discrete dipole approximation is utilized to calculate the single-scattering properties of the mixed-phase particles throughout the melting process. Then, the properties of the particles are “mapped” into simpliRed microphysical simulations of particle size spectra in the melting layers of stratiform, precipitating clouds. The bulk single-scattering properties of the melting layers and the sensitivity of their properties to modeling assumptions are explored, and the implications for combined radar-radiometer precipitation remote sensing from GPM are discussed.

William S Olson↗
NASA NTRS1993

Fe/Mn in olivine of carbonaceous meteorites

Olivines in primitive meteorites show a range of Fe/Mn both within one grain and among grains suggesting that they have recorded changing conditions during or after growth. Because olivine should be an early forming phase, Fe/Mn is used here to infer these earliest conditions. Initial Fe/Mn in cores of isolated, euhedral forsterite in both C2 and C3 meteorites ranges from 25 to 35 but differs at grain edge. Murchison (C2) forsterites show Fe/Mn approaching 1.0 at the grain edge while Ornans Fe/Mn is near 60 at grain edge. These values are lower than the matrix Fe/Mn for both meteorites and the distinct difference in zoning profile indicates different processes operating during and after grain growth. The Fe/Mn of bulk samples from a particular source such as the Moon is nearly constant. Individual samples show variation suggesting that there is some fractionation of Mn from Fe. Minerals have their individual ranges of Fe/Mn which has been used to recognize different types of olivine within one meteorite. Extreme values of Fe/Mn below 1.0 occur in forsterite from some IDP's, UOC matrix, and C1 meteorites. There are apparently no detailed studies of Fe/Mn variation within single olivine grains. Forsterite grains in C2 and C3 carbonaceous chondrites show complex zoning, and the nearly pure forsterites (Fo greater than approximately 99.5) have high levels of some minor elements including Ti, Al, V, and Sc. There is disagreement on the original source of these grains and both chondrule and vapor growth have been proposed. In addition, there is clear evidence that diffusion has affected the outer margins but in some cases the whole grain. Within the cores, the FeO range is limited, and if growing under constant conditions, the Fe/Mn should be near constant as there is little fractionation of Mn from Fe by forsterite. Additionally, there are apparently no co-crystallizing phases as evidenced by a lack of common inclusions in the forsterites. These observations are now followed by analyses of isolated olivine grains in C2 and C3 meteorites.

Steele, Ian M.↗
NASA NTRS1977

ESR studies of the slow tumbling of vanadyl spin probes in nematic liquid crystals

ESR line shapes that are appropriate for slowly tumbling vanadyl spin probes in viscous nematic liquid crystals were calculated by the stochastic Liouville method. Because of the symmetry possessed by vanadyl, the analysis and interpretation of these line shapes was simplified considerably. Spectral line shapes agreed well with experimental spectra of VOAcAc in the nematic liquid crystal Phase V and BEPC. Deviations from Brownian rotational diffusion were noted. A slowly fluctuating torque analysis yielded good agreement with the experimental spectra.

Eastman, M. P.↗
NASA NTRS1977

Slowly cooled microgabbros 15555 and 15065

An experimental study involving equilibration of Apollo 15 samples 15555 and 15065 in high-purity iron capsules is described. Comparison of mineral zoning trends with the experimental sequence suggests that the early crystallizing phases in the rock maintained surface equilibrium with the liquid. Olivine and pyroxene chemistry indicates that 15555 cooled slightly more rapidly than 15065, which cooled at approximately 0.2-0.3 C/day. It is suggested that 15065 and 15555 represent liquid compositions, and that these liquids appear to have been fractionated during ascent through the crust (15065), or to have been derived from an olivine-pyroxene source (15555) with Fe/(Fe + Mg) approximately equal to 0.73 at a depth between 150-200 km.

Walker, D.↗
NASA NTRS1979

A summary of the petrology and geochemistry of pristine highlands rocks

The petrology and geochemistry of pristine lunar highlands rock samples consisting of ferroan anorthosites, norites, troctolites, spinel troctolites/dunite/lherzolite, and KREEP, are described. In addition, petrographic and chemical evidence is presented which shows that low-siderophile rocks are the result of endogenous igneous activity and not impact melt differentiation. For example, these rocks contain Fe-metal as a late-crystallizing phase, and have W/La ratios higher than polymict breccias.

Norman, M. D.↗