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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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At least 145 records · Page 8

Liquid Methane Testing With a Large-Scale Spray Bar Thermodynamic Vent System

NASA's Marshall Space Flight Center conducted liquid methane testing in November 2006 using the multipurpose hydrogen test bed outfitted with a spray bar thermodynamic vent system (TVS). The basic objective was to identify any unusual or unique thermodynamic characteristics associated with densified methane that should be considered in the design of space-based TVSs. Thirteen days of testing were performed with total tank heat loads ranging from 720 to 420 W at a fill level of approximately 90%. It was noted that as the fluid passed through the Joule-Thompson expansion, thermodynamic conditions consistent with the pervasive presence of metastability were indicated. This Technical Publication describes conditions that correspond with metastability and its detrimental effects on TVS performance. The observed conditions were primarily functions of methane densification and helium pressurization; therefore, assurance must be provided that metastable conditions have been circumvented in future applications of thermodynamic venting to in-space methane storage.

Hastings, L. J.↗

Modeling the dynamic response of rock masses with multiple compliant fluid saturated joint sets—Part I: Mesoscale simulations

Recently a mesoscale model was developed that includes thermomechanically consistent constitutive equations with dissipation due to porous compaction, inelastic distortional deformation rate, and slipping on persistent dry joint surfaces. In this Part I of a two-part paper, we describe enhancements of the mesoscale model which include: normal compliance with hysteresis, non-persistent joints with finite area, joint sets with angular deviation, and the weakening effect of fluid pressure in the joints. Examples study the influences of these effects on average strength. These computationally expensive simulations are used to inspire functional forms in a continuum model, described in Part II, which is needed for large scale simulations of real applications.

42 ENGINEERING↗

Formation, cooling history and age of impact events on the IIE iron parent body: Evidence from the Miles meteorite

Most iron meteorites formed in planetary cores during differentiation, but the IIE iron meteorites have chemical and physical features that are inconsistent with this origin. By combining mineral chemistry, mineral modes and three-dimensional petrography, we reconstruct the bulk chemistry of the felsic silicate-bearing Miles IIE iron meteorite and demonstrate that the silicate inclusion compositions are similar to partial melts produced experimentally from an H chondrite composition. We use the reconstructed bulk composition, mineralogy and thermodynamic modelling to show that melting above ~ 1200°C under reducing conditions formed metal (Fe-Ni alloy) and felsic silicate partial melts. Upon cooling, the melts crystallized Mg-rich pyroxenes, Na- and K-rich feldspars, and tridymite. Importantly, this mechanism enriches cosmochemically volatile elements (i.e., those with a 50% condensation temperature of ~430–830°C, like Na and K) to the level found in the felsic silicate inclusions. The presence of crystallographically disordered srilankite (only stable above 1160°C) and an absence of Widmanstätten texture require both high peak temperatures and rapid cooling, which cannot be explained by core formation. Instead, they point to small melt volumes, a transient heat pulse, and small thermal mass, and imply efficient physical segregation of silicate and metallic melts through buoyancy separation followed by rapid cooling that arrested the separation of metal and silicate liquid phases. In situ 207 Pb/ 206 Pb age of 4542.3 ± 4.0 Ma in Zr-oxide and phosphate minerals dates the melting event that formed the silicate inclusions. This age aligns with the earliest ages found in other IIE iron meteorite silicates and requires a heating event ~25 million years after the solar system formed. We found 39 Ar/ 40 Ar ages of 3495 ± 52 Ma (low-T) and 4303 ± 7 Ma (high-T) in a K-feldspar grain, with the 3495 Ma age aligning with later thermal events recorded in other IIE iron meteorites. Dating reveals the complex petrogenetic and thermal history of Miles and the IIE iron meteorites. This is the first IIE iron meteorite found to record evidence of heating at 4.5 and 3.5 Ga likely from impact events. We propose that high-velocity impact(s) into an iron-rich, porous chondritic parent body at ~4.54 Ga produced immiscible metal and silicate melts that cooled rapidly and trapped low density silicate inclusions within high density metal. Other IIE irons that formed at lower peak temperatures (900–1000°C) contain chondritic silicate inclusions and relict chondrules, supporting this conceptual model. In conclusion, this petrogenesis is consistent with thermodynamic modelling, experimental data and the wide range of peak temperatures and cooling rates observed in the IIE iron meteorites.

58 GEOSCIENCES↗

Compatibility of SiC with ODS FeCrAl in flowing Pb-Li at 600° - 700°C

To establish the maximum operating temperature for the dual coolant lead lithium (DCLL) blanket concept, thermal convection loop (TCL) experiments were conducted for 1000 h with a peak temperature of 700 °C to determine compatibility with commercial eutectic Pb~17at.%Li. Two TCLs were fabricated from alloy APMT (FeCrAlMo) and the baseline TCL experiment contained only APMT specimens. The second TCL experiment exposed more fusion relevant CVD SiC and ODS Fe-10Cr-6Al specimens in the hot and cold legs. In the second experiment, the mass losses were much larger for the ODS FeCrAl specimens and most of the CVD SiC specimens experienced a mass gain as SiC reacted to form an Fe- and Cr-rich carbide reaction product. Dissolved Fe and Cr reacted with the SiC and removing Fe and Cr from the liquid appeared to increase ODS FeCrAl dissolution. Such a dissimilar material interaction appears consistent with thermodynamic calculations. Significant attack at the top of the hot leg in both experiments suggests that the Pb-Li compatibility of FeCrAl alloys is inadequate at 700 °C in a flowing environment and the maximum PbLi temperature is < 675 °C.

36 MATERIALS SCIENCE↗

Halide Vapor Phase Epitaxy of Ge from an Elemental Source

Halide vapor phase epitaxy shows promise for low-cost photovoltaic device manufacturing because of its high growth rates and lower cost elemental precursors but previously has not been used to deposit epitaxial Ge. Here, we demonstrate Ge deposition by generating GeCl 2 in situ from solid Ge and HCl in a N 2 ambient. To achieve Ge growth, we inject AsH 3 and PH 3 as sources of active hydrogen to the growth surface to create a driving force for growth. We do not observe Ge growth unless a supply of hydrogen is added, consistent with thermodynamic calculations. Furthermore, we show the hydrogen source must crack readily on the substrate surface to enable growth; relatively stable sources such as H 2 do not cause growth. Unintentional group V doping is one drawback of using AsH 3 and PH 3 to drive the Ge reaction. We observed As or P concentrations in the Ge films ranging from 4 x 10 17 to 1 x 10 18 atoms/cm 3 , concentrations that can drastically influence device characteristics. However, we note there are numerous other "helper molecule" options that can provide active hydrogen without doping or etching the material. This work provides a path forward for Ge deposition for optoelectronic devices from an elemental source.

14 SOLAR ENERGY↗

Altered Stability and Degradation Pathway of CH 3 NH 3 PbI 3 in Contact with Metal Oxide

Degradation in CH 3 NH 3 PbI 3 (MAPbI 3 ), when in contact with commonly used metal oxide transport layer materials in optoelectronic devices, is explored experimentally and theoretically. On the basis of the decomposition temperature, the interfacial stability decreases in the following order: MAPbI 3 + TiO 2 ~ MAPbI 3 alone > MAPbI 3 + SnO 2 > MAPbI 3 + NiO, consistent with thermodynamic data. When MAPbI 3 contacts NiO or SnO 2 , experimental results unequivocally show interfacial decomposition occurs at a lower temperature than bulk decomposition and produces different degradation products. Density functional theory calculations reveal an altered reaction pathway on oxide surfaces and elucidate the difference between NiO and TiO 2 . Furthermore, these results pinpoint the importance of understanding the interaction between halide perovskite and other materials used in a device to achieve intrinsically stable devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reconciling and Improving Formulations for Thermodynamics and Conservation Principles in Earth System Models (ESMs)

Abstract This paper provides a comprehensive derivation of the total energy equations for the atmospheric components of Earth System Models (ESMs). The assumptions and approximations made in this derivation are motivated and discussed. In particular, it is emphasized that closing the energy budget is conceptually challenging and hard to achieve in practice without resorting to ad hoc fixers. As a concrete example, the energy budget terms are diagnosed in a realistic climate simulation using a global atmosphere model. The largest total energy errors in this example are spurious dynamical core energy dissipation, thermodynamic inconsistencies (e.g., coupling parameterizations with the host model) and missing processes/terms associated with falling precipitation and evaporation (e.g., enthalpy flux between components). The latter two errors are not, in general, reduced by increasing horizontal resolution. They are due to incomplete thermodynamic and dynamic formulations. Future research directions are proposed to reconcile and improve thermodynamics formulations and conservation principles.

54 ENVIRONMENTAL SCIENCES↗

Episodic Magma Hammers for the 15 January 2022 Cataclysmic Eruption of Hunga Tonga‐Hunga Ha'apai

Understanding the forces and magma system dynamics on timescales of seconds to minutes remains challenging. In the January 2022 phreatoplinian Hunga Tonga-Hunga Ha'apai eruption, four remarkably similar seismic subevents within a 5-min interval occurred during the intensifying early eruptive phase. The subevents are similar in waveforms and durations (~25 s each). Each subevent begins with an unusual negative P-wave polarity which is inferred, using full-wave seismic modeling, to be caused by an upward single-force mechanism at the volcano created by a magma hammer likely in response to magma flow blockage/constriction during the early part of the eruption as discharge rapidly increased over orders of magnitude with concomitant conduit geometry evolution and instability. Our proposed episodic magma hammer model is consistent with thermodynamic and phase properties of the magmatic mixture, and yields an estimate of conduit mass flow in agreement with vent discharge rates derived from satellite imagery of plume heights.

58 GEOSCIENCES↗

Observation of Joule–Thomson photon-gas expansion

In recent years, a self-consistent optical thermodynamic framework has emerged that offers a systematic methodology to understand, harness and exploit the complex collective dynamics of multimode nonlinear systems. These developments now allow consideration of a series of longstanding problems in optics, including the prospect of funnelling the entire power flowing in a multimode system into its ground state, for which no methodology currently exists. Here, we demonstrate an all-optical Joule-Thomson expansion process mediated by photon-photon interactions whereby the temperature of the optical gas drops abruptly to zero. Our experiments in various configurations of coupled multicore nonlinear waveguide arrangements illustrate how light undergoing expansion-induced cooling can be channelled from arbitrary input states into the fundamental mode with near-unity efficiency. We show that the stability of the post-expansion state is ensured through an irreversible process of energy conversion. The all-optical thermodynamic phenomena explored in this study may enable innovative techniques where various uncorrelated but identical sources are merged into a unified spatially coherent state, offering a route for direct beam combining.

Kirsch, Marco S. (ORCID:0000000342798228)↗

Investigations of the stability of GaAs for photoelectrochemical H 2 evolution in acidic or alkaline aqueous electrolytes

The long-term stability of p-GaAs photocathodes has been investigated for the hydrogen-evolution reaction (HER) in contact with either 1.0 M H 2 SO 4 (aq) or 1.0 M KOH(aq). Stability for the HER was evaluated using p-GaAs electrodes that were either etched or coated with active HER catalysts (Pt and CoP). Changes in surface characteristics of GaAs after exposure to electrochemical conditions were monitored by X-ray photoelectron spectroscopy (XPS), and electrode dissolution processes were evaluated by inductively coupled plasma mass spectrometry (ICP-MS). Consistent with thermodynamic predictions, after operation of the HER at pH 0 or pH 14, illuminated etched p-GaAs electrodes exhibited minimal dissolution while preserving a nearly stoichiometric surface. Electrodeposition or sputtering of Pt on the p-GaAs surface promoted the formation of excess As 0 via an interfacial reaction during the HER. The resulting non-stoichiometric As 0 -rich surface of p-GaAs/Pt electrodes caused a loss in photoactivity as well as substantial cathodic dark current. In contrast, p-GaAs electrodes coated with thin-film CoP catalysts did not display an increase in surficial As 0 after operation of the HER in acidic electrolytes. Minimization of deleterious interfacial reactions is thus critical to obtain extended stability in conjunction with high performance from p-GaAs photocathodes.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Octupolar versus Néel Order in Cubic 5d 2 Double Perovskites

We report time-of-flight neutron spectroscopy and neutron and x-ray diffraction studies of the 5 d 2 double perovskite magnets, Ba 2 M OsO 6 ( M = Zn , Mg , Ca ). We find that these materials host antiferromagnetically coupled 5 d 2 Os 6 + ions decorating a face-centered cubic (fcc) lattice and are found to remain cubic down to the lowest temperatures. They all exhibit thermodynamic anomalies consistent with a single phase transition at a temperature T * , and a gapped magnetic excitation spectrum with spectral weight concentrated at wave vectors typical of type-I antiferromagnetic orders. However, while muon spin resonance experiments show clear evidence for time-reversal symmetry breaking below T * , we observe no corresponding magnetic Bragg scattering signal. These results are shown to be consistent with ferro-octupolar symmetry breaking below T * , and are discussed in the context of other 5 d double perovskite magnets and theories of exotic orders driven by multipolar interactions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Sulfur speciation in dacitic melts using X-ray absorption near-edge structure spectroscopy of the S K -edge (S-XANES): Consideration of radiation-induced changes and the implications for sulfur in natural arc systems

Abstract The synchrotron technique of micro X-ray absorption near-edge structure spectroscopy at the sulfur K-edge (S-XANES) provides a unique opportunity to measure the proportion of different oxidation states of sulfur (S) in silicate glasses. Although applied extensively in the analysis of basaltic silicate glasses, few S-XANES studies have investigated variations in S oxidation states with fO2 in felsic silicate glasses. In addition, no study has systematically compared the S-XANES results obtained from the same samples at different photon flux densities to quantify the relationship between exposure time and changes in S speciation in silicate glass, as has been done for Fe and V. This study evaluates observed differences in S speciation measured in experimentally produced H2O-saturated dacitic glasses over a range of reducing to oxidizing conditions (from log fO2 = ΔFMQ-0.7 to ΔFMQ+3.3; FMQ is the fayalite-magnetite-quartz mineral redox buffer) and equilibrated at 1000 °C and 300 MPa. S-XANES spectra were collected at three different photon flux densities using three microspectroscopy beamlines. As is observed in S-XANES analyses of basaltic silicate glasses, beam-induced changes to the S6+/ΣS are observed as a function of photon flux density and beam exposure time. Our results demonstrate that silicate glasses of dacitic composition undergo beam-induced photo-reduction in samples equilibrated at ΔFMQ > +1.75 and photo-oxidation if equilibrated at ΔFMQ < +1. The time required to observe beam-induced changes in the spectra varies as a function of flux density, and our study establishes an upper photon density limit at ~1.0 × 1012 photons/µm2. The S6+/ΣS calculated from spectra collected below this absorbed photon limit at intermediate flux densities (~1–4 × 109 photons/s per µm2) are affected by beam damage, as no conditions were found to be completely free of beam-induced changes. However, the S6+/ΣS ratios calculated below the limit at intermediate flux densities are consistent with thermodynamic constraints, demonstrating that S6+/ΣS ratios calculated from S-XANES spectra can be considered reliable for estimating the oxygen fugacity. Our results carry important implications for the S budget of felsic magmas and dissolution mechanisms in evolved melts. While our results from all three flux densities show the presence of S4+ dissolved in relatively oxidized (ΔFMQ > +1.75) dacitic glass, even in the spectra exposed to the lowest photon densities, we are unable to rule out the possibility that the S4+ signal is the result of instantaneous X-ray irradiation induced beam damage using S-XANES alone. When our spectra are compared to S-XANES spectra from basaltic silicate glasses, important differences exist in the solubility of S2– and S6+ between dacitic silicate melts, pointing to differences in solubility mechanisms as melt composition changes. This study highlights the need for further investigation into beam damage systematics, presence of S4+, and the solubility mechanisms of different oxidation states of S as silicate melt composition changes.

Geochemistry & Geophysics↗

Effect of Anoxic Iron Corrosion on WIPP Brine Geochemistry FY23 Final Report (U)

A 280-day study was completed to evaluate the effect of zero-valent iron (Fe 0 ) on the Waste Isolation Pilot Plant (WIPP) brine geochemistry under anticipated reducing conditions. Hydrogen (H 2 ) gas is expected to be present in the repository after closure due to the anoxic corrosion of a vast quantity of iron contained in the waste forms disposed at WIPP; therefore, a background argon atmosphere containing H 2 was chosen for this study. WIPP groundwater brine pH and E h will impact the mobility and fate of plutonium within the repository. Modeling and laboratory results for Castile WIPP brine indicate that equilibrium E h values relative to the standard hydrogen electrode (SHE) are 40 mV more reducing (i.e., more negative) than those for Salado WIPP brine (-480 mV vs. -440 mV, respectively) because of the higher pH of the Castile brine (pH 9.3 for Castile vs. pH 8.8 for Salado). The E h and pH data were corrected for the effects of high ionic strength. The experimental results for both brines are consistent with thermodynamic predictions using OLI Systems' Mixed Solvent Electrolyte chemical equilibrium model. The measured and corrected pH and E h data from this study are provided in Table ES-1 and Table ES-2, respectively.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

University of Kentucky measurements of wind, temperature, pressure and humidity in support of LAPSE-RATE using multisite fixed-wing and rotorcraft unmanned aerial systems

In July 2018, unmanned aerial systems (UASs) were deployed to measure the properties of the lower atmosphere within the San Luis Valley, an elevated valley in Colorado, USA, as part of the Lower Atmospheric Profiling Studies at Elevation – a Remotely-piloted Aircraft Team Experiment (LAPSE-RATE). Measurement objectives included detailing boundary layer transition, canyon cold-air drainage and convection initiation within the valley. Details of the contribution to LAPSE-RATE made by the University of Kentucky are provided here, which include measurements by seven different fixed-wing and rotorcraft UASs totaling over 178 flights with validated data. The data from these coordinated UAS flights consist of thermodynamic and kinematic variables (air temperature, humidity, pressure, wind speed and direction) and include vertical profiles up to 900 m above the ground level and horizontal transects up to 1500 m in length. These measurements have been quality controlled and are openly available in the Zenodo LAPSE-RATE community data repository (https://zenodo.org/communities/lapse-rate/, last access: 23 July 2020), with the University of Kentucky data available at https://doi.org/10.5281/zenodo.3701845 (Bailey et al., 2020).

54 ENVIRONMENTAL SCIENCES↗

Cavitation in liquid cryogens. 1: Venturi

The results of continuing cavitation studies are reported. The cavitation characteristics of liquid hydrogen and liquid nitrogen flowing in a transparent plastic Venturi are discussed. Thermodynamic data, consisting of pressure and temperature measurements within fully developed hydrogen cavities, are reported. Details concerning test apparatus, test procedure, and data correlation techniques are given.

Hord, J.↗

An interactive graphics program to retrieve, display, compare, manipulate, curve fit, difference and cross plot wind tunnel data

The Aerodynamic Data Analysis and Integration System (ADAIS), developed as a highly interactive computer graphics program capable of manipulating large quantities of data such that addressable elements of a data base can be called up for graphic display, compared, curve fit, stored, retrieved, differenced, etc., was described. The general nature of the system is evidenced by the fact that limited usage has already occurred with data bases consisting of thermodynamic, basic loads, and flight dynamics data. Productivity using ADAIS of five times that for conventional manual methods of wind tunnel data analysis is routinely achieved. In wind tunnel data analysis, data from one or more runs of a particular test may be called up and displayed along with data from one or more runs of a different test. Curves may be faired through the data points by any of four methods, including cubic spline and least squares polynomial fit up to seventh order.

Elliott, R. D.↗

Molybdenite in calcium-aluminum-rich inclusions in the Allende meteorite

The first observations of molybdenite in a meteorite have been made in two Ca-Al-rich inclusions in the Allende chondrite. The mineral occurs as single individuals completely enclosed in high Ni metal (62-64.5 wt. % Ni). The association with refractories is consistent with thermodynamic calculations which predict that Mo is a high temperature condensate even when nucleation constraints are imposed on the formation of a metal phase. Kinetic factors (including nucleation constraints) appear to have played an important role in the formation of molybdenite and the associated sulfides, magnetite and high nickel metal.

Fuchs, L. H.↗