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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 469 records · Page 26

Isotropic-to-Nematic Transition in Salt-Free Polyelectrolyte Coacervates from Coarse-Grained Simulations

Recent interest in complex coacervation between oppositely charged polyelectrolytes (PEs) has been fueled by its relevance to biology in the context of membraneless organelle formation within living cells. For PEs with limited flexibility (such as double-stranded DNA), theoretical treatments and recent experiments have reported the emergence of liquid crystalline order (LCO) within the resulting coacervate phases. In this work, we study the underlying physics of this phenomenon using coarse-grained molecular dynamics simulations of symmetric semiflexible-semiflexible and asymmetric semiflexible-flexible coacervates. By comparing coacervates with the corresponding semidilute solutions of neutral polymers, we demonstrate that the presence of Coulomb interactions in coacervates facilitates orientational ordering, in agreement with theoretical predictions. Quantitative comparisons between our simulations and theory indicate that, for asymmetric nematic coacervates, the strong orientational ordering of stiff polyanions induces a weak ordering of the flexible polycations-an effect that was not anticipated by available theoretical studies. Simulations reveal that, for nematic coacervates, the preferred orientation of the PE chains at the liquid-liquid coacervate-supernatant interface is parallel, and the alignment of semiflexible PEs is homogeneous. The results presented here provide new molecular-level insights into the intracoacervate LCO and will help motivate further experimental and theoretical activities in this area.

36 MATERIALS SCIENCE↗

A Forward-Looking Dataset of EV Managed Charging Resource and Costs

This presentation summarizes a high-resolution, forward-looking dataset of EV adoption, EV charging, and managed charging resource. Vehicle-level data are grounded in current adoption and charging patterns, and ~200,000 real-world vehicle-weeks of travel data covering all on-road segments (i.e., light-duty, transit and school buses, local, regional and long-haul medium- and heavy-duty). The data, which include multiple charging profiles per vehicle to bound flexibility, are then processed and aggregated to describe baseline charging and charge management resource by county, hour, year, scenario, and vehicle type. Coupled with one of four scenarios of how EV managed charging costs might evolve over time, the dataset enables a power sector capacity expansion model to select cost-optimal quantities of EV managed charging and supply-side resources to reliably satisfy demand. Five integration strategies: Baseline, Daytime and Flat (passive), Flex (active), and Stress (anti-strategy), illustrate how baseline charging and flexibility potential changes with EVSE build-out and charging preferences.

33 ADVANCED PROPULSION SYSTEMS↗

[Results of Simulation Studies]

Lattice Monte Carlo and off-lattice molecular dynamics simulations of h(sub 1)t(sub 4) and h(sub 4)t(sub l) (head/tail) amphiphile solutions have been performed as a function of surfactant concentration and temperature. The lattice and off-lattice systems exhibit quite different self-assembly behavior at equivalent thermodynamic conditions. We found that in the weakly aggregating regime (no preferred-size micelles), all models yield similar micelle size distributions at the same average aggregation number, albeit at different thermodynamic conditions (temperatures). In the strongly aggregating regime, this mapping between models (through temperature adjustment) fails, and the models exhibit qualitatively different micellization behavior. Incipient micellization in a model self-associating telechelic polymer solution results in a network with a transient elastic response that decays by a two-step relaxation: the first is due to a heterogeneous jump-diffusion process involving entrapment of end-groups within well-defined clusters and this is followed by rapid diffusion to neighboring clusters and a decay (terminal relaxation) due to cluster disintegration. The viscoelastic response of the solution manifests characteristics of a glass transition and entangled polymer network.

Source record↗

The H-poor nature of incompletely melted planetesimals: The view from acapulcoites and lodranites

The abundance of H in planetary building blocks is of fundamental importance for constraining the evolution of the terrestrial planets. It is commonly assumed that chondrites are the principal sources of Earth’s H; however, recent studies have suggested that primitive achondrites and achondrites may retain a small complement of H. There are few constraints on the H budgets of primitive achondrites, which represent the transition from unmelted to melted planetesimals, but prior work suggests that bulk parent body H contents are several orders of magnitude lower than typical chondritic values. Therefore, to provide further constraints on H retention during the transition from unmelted to melted planetesimals, we have measured the H contents of olivine, orthopyroxene, clinopyroxene, and plagioclase from a suite of acapulcoite-lodranite clan meteorites. Acapulcoite-lodranite clan meteorites represent the “prototypical” primitive achondrite parent body and have bulk major element compositions more akin to the Earth than previously studied primitive achondrites (e.g., the ureilites). We find that the H 2 O contents of olivine (∼5–12 µg/g H 2 O), orthopyroxene (∼3–10 µg/g H 2 O), and clinopyroxene (∼5–8 µg/g H 2 O) are broadly similar, while plagioclase (∼2.5–5 µg/g H 2 O) tends to be offset to lower values. Using a simple, single-stage batch-melting model, we calculate a preferred maximum acapulcoite-lodranite parent body H 2 O content of 38 µg/g, which is similar to other estimates for primitive achondritic and achondritic parent bodies. Furthermore, assuming chondrite-like precursor materials, our data are consistent with efficient loss of H prior to or during the onset of melting of early-formed planetesimals. This requires that Earth’s H-budget was dominated by building blocks that underwent minimal thermal processing.

Primitive achondrite↗

Amapari Marker Band Metal‐Enrichments: Potential Mechanisms and Implications for Surface and Subsurface Water and Weathering in Gale Crater

NASA's Curiosity rover is exploring a 5 km tall sedimentary mound that is hypothesized to record the transition from a warm and wet (phyllosilicate-rich) to a cold and drier (sulfate-rich) Mars. Evidence of magnesium sulfate-bearing rock has shown that Curiosity has crossed through this phyllosilicate-sulfate transition. Recently, Curiosity arrived at the Amapari Marker Band, a darker, indurated unit that can be traced laterally for tens of kilometers in orbiter images. Here, Curiosity found evidence for a very broad lake, and bedforms interpreted as wave-ripple laminated sedimentary rock that likely was deposited in shallow water in the explored location, before becoming a deeper lake. These rocks are enriched in Fe, Mn, and Zn which has major implications for groundwater paleohydrology in Gale crater. Three formation hypotheses are considered: concretion formation during early diagenetic alteration of shallow lake sediments, laterization or leaching of the sediments, and addition of Fe, Mn, and Zn by a mildly acidic and reducing groundwater interacting with a redox and/or pH front in a stratified lake. The preferred interpretation of the metal enrichments within the Amapari Marker band sedimentary rocks is that they formed in a shallow water environment at a redox and/or pH front within the ripple unit, which drove precipitation and concentration of metals. If the enrichments are due to groundwater alteration, these processes could link subsurface and surface environments. Water and the presence of high amounts of redox sensitive elements and other metals are favorable indicators for habitability.

58 GEOSCIENCES↗

Effects of interstitial oxygen on ω transformations and twin formation in bcc NbTaTiHf multi-principal element alloy from first-principles

Transformation- and twinning-induced plasticity (TRIP and TWIP) have been reported to contribute to the low-temperature deformation of some body-centered cubic (bcc) multi-principal element alloys (MPEAs) containing large fractions of group IV transition metals. The influence of interstitial solutes on the mechanisms underlying these forms of plasticity, however, remains unclear. Using first-principles calculations, we study the effects of interstitial O atoms on the relative stability of bcc and ω phases and on unstable and twin boundary stacking fault energy profiles in a representative bcc MPEA with high group-IV elemental fraction: NbTaTiHf. We find that O additions generally promote the relaxation of ω configurations back to their parent bcc structure, therefore inhibiting ω transformation. Calculations of the Rice parameter for bulk bcc and phases, as well as bcc-ω interfaces, further show that ω formation is a potent embrittlement factor, an effect that is enhanced by O additions, suggesting that the formation of bcc-ω interfaces is energetically preferred over the formation of the bulk ω phase. By contrast, the Rice parameter for twin boundaries indicates that these interfaces do not embrittle the material, even with O atoms at twin boundaries, providing a more favorable pathway for plastic deformation compared to ω transformation.

Density functional theory↗

Low Melt Viscosity Resins for Resin Transfer Molding

In recent years, resin transfer molding (RTM) has become one of the methods of choice for high performance composites. Its cost effectiveness and ease of fabrication are major advantages of RTM. RTM process usually requires resins with very low melt viscosity (less than 10 Poise). The optimum RTM resins also need to display high thennal-oxidative stability, high glass transition temperature (T(sub g)), and good toughness. The traditional PMR-type polyimides (e.g. PMR-15) do not fit this requirement, because the viscosities are too high and the nadic endcap cures too fast. High T(sub g), low-melt viscosity resins are highly desirable for aerospace applications and NASA s Reusable Launch Vehicle (RLV) program. The objective of this work is to prepare low-melt viscosity polyimide resins for RTM or resin film infusion (RFI) processes. The approach involves the synthesis of phenylethynyl-terminated imide oligomers. These materials have been designed to minimize their melt viscosity so that they can be readily processed. During the cure, the oligomers undergo both chain extension and crosslinking via the thermal polymerization of the phenylethynyl groups. The Phenylethynyl endcap is preferred over the nadic group due to its high curing temperature, which provides broader processing windows. This work involved the synthesis and polymerization of oligomers containing zig-zag backbones and twisted biphenyl structures. Some A-B type precursors which possessed both nitro and anhydride functionality, or both nitro and amine functionality, were also synthesized in order to obtain the well defined oligomers. The resulting zig-zag structured oligomers were then end-capped with 4-phenylethynylphthalic anhydride (PEPA) for further cure. The properties of these novel imide oligomers are evaluated.

Harris, Frank W.↗

Incorporation of EGPWS in the NASA Ames Research Center 747-400 Flight Simulator

The NASA Ames Research Center CAE Boeing 747300 flight simulator is used primarily for the study of human factors in aviation safety. The simulator is constantly upgraded to maintain a configuration match to a specific United Airlines aircraft and maintains the highest level of FAA certification to ensure credibility to the results of research programs. United's 747-400 fleet and hence the simulator are transitioning from the older Ground Proximity Warning System (GPWS) to the state-of-the-art Enhanced Ground Proximity Warning System (EGPWS). GPWS was an early attempt to reduce or eliminate Controlled Flight Into Terrain (CFIT). Basic GPWS alerting modes include: excessive descent rate, excessive terrain closure rate, altitude loss after takeoff, unsafe terrain clearance, excessive deviation below glideslope, advisory callouts and windshear alerting. However, since GPWS uses the radar altimeter which looks straight down, ample warning is not always provided. EGPWS retains all of the basic functions of GPWS but adds the ability to look ahead by comparing the aircraft position to an internal database and provide additional alerting and display capabilities. This paper evaluates three methods of incorporating EGPWS in the simulator and describes the implementation and architecture of the preferred option.

Sallant, Ghislain↗

Enhancing MnBi 2 Te 4 Stability by Doping

MnBi 2 Te 4 (MBT) is an intrinsically magnetic topological material that possesses unique properties due to the quantum Hall effect. However, the low Mn–Bi mixed antisite formation energy is detrimental to these properties as it alters the long-range magnetic ordering in the Mn layer. Therefore, it is crucial to destabilize the antisite defects in MBT while preserving the favorable electronic properties. Here, to this end, we utilized a screening approach to understand the role of dopants in the Mn and Bi sites. We find that Sc, Y, and La dopings prefer substitutions on the Bi site and significantly increase the Mn–Bi antisite defect formation energy. We find that the contribution from the empty s and d states of Sc, Y, and La around the Fermi level is insignificant. However, at the high concentration limit, the Bi–Te octahedra are significantly modified with doping, leading to important changes in the band structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A model El Nino-Southern Oscillation

A coupled atmosphere-ocean model is developed and used to study the ENSO (El Nino/Southern Oscillation) phenomenon. With no anomalous external forcing, the coupled model reproduces certain key features of the observed phenomenon, including the recurrence of warm events at irregular intervals with a preference for three to four years. It is shown that the mean sea surface temperature, wind and ocean current fields determine the characteristic spatial structure of ENSO anomalies. The tendency for phase-locking of anomalies is explained in terms of a variation in coupling strength associated with the annual cycle in the mean fields. Sensitivity studies reveal that both the amplitude and the time scale of the oscillation are sensitive to several parameters that affect the strength of the atmosphere-ocean coupling. Stronger coupling implies larger oscillations with a longer timescale. A critical element of the model oscillation is the variability in the equatorial heat content of the upper ocean. Equatorial heat content increases prior to warm events and decreases sharply during the events. A theory for this variability and the associated transitions between non-El Nino and El Nino states is presented. Implications of the model results for the prediction of El Nino events are discussed.

Zebiak, Stephen E.↗

Band Gap Engineering and Metastable Phase Discovery in Cu 2 BaSnS 4– x Se x Nanocrystals via Topotactic Anion Exchange

Earth-abundant multinary inorganic chalcogenides, such as Cu 2 BaSnS 4–x Se x (CBTSSe), have emerged as promising absorbers for next-generation solar cells. However, accessing colloidal CBTSSe nanocrystals, including metastable polymorphs with more favorable optoelectronic properties, remains a critical synthetic challenge. Herein, we report the first use of topotactic anion exchange to access metastable crystal structures in soft chemistry syntheses. By varying the stoichiometry of selenium precursors, we directly synthesize Cu 2 BaSnS 4–x Se x (0 ≤ x ≤ 4) nanocrystals with a broad band gap tunability of 1.51–2.04 eV. At x = 4, a new metastable trigonal phase of Cu 2 BaSnSe 4 is isolated. This phase arises via an in-situ topotactic anion exchange from sulfur-rich Cu 2 BaSnS 4–x Se x intermediates, while retaining both the cation sublattice and overall nanocrystal morphology. The trigonal Cu 2 BaSnSe 4 exhibits a nearly direct band gap that is 280 meV lower than its thermodynamically stable orthorhombic counterpart, aligning more closely with the optimal band gap for single-junction solar cells. In contrast, a post-synthetic anion exchange route leads to the thermodynamically preferred orthorhombic polymorph, pointing to the critical nature of the in-situ transformation. Our findings open a versatile pathway for both polymorphic and morphological control in colloidal nanocrystals, expanding the synthetic design space for new optoelectronic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Binding of carboxylate and water to monovalent cations

The interactions of carboxylate anions with water and cations are important for a wide variety of systems, both biological and synthetic. Here, in order to gain insight on properties of the local complexes, we apply density functional theory, to treat the complex electrostatic interactions, and investigate mixtures with varied numbers of carboxylate anions (acetate) and waters binding to monovalent cations, Li + , Na + and K + . The optimal structure with overall lowest free energy contains two acetates and two waters such that the cation is four-fold coordinated, similar to structures found earlier for pure water or pure carboxylate ligands. More generally, the complexes with two acetates have the lowest free energy. In transitioning from the overall optimal state, exchanging an acetate for water has a lower free energy barrier than exchanging water for an acetate. In most cases, the carboxylates are monodentate and in the first solvation shell. As water is added to the system, hydrogen bonding between waters and carboxylate O atoms further stabilizes monodentate structures. These structures, which have strong electrostatic interactions that involve hydrogen bonds of varying strength, are significantly polarized, with ChelpG partial charges that vary substantially as the bonding geometry varies. Overall, these results emphasize the increasing importance of water as a component of binding sites as the number of ligands increases, thus affecting the preferential solvation of specific metal ions and clarifying Hofmeister effects. Finally, structural analysis correlated with free energy analysis supports the idea that binding to more than the preferred number of carboxylates under architectural constraints are a key to ion transport.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Temperature-dependent growth of hexagonal and monoclinic gallium sulfide films by pulsed-laser deposition

We demonstrate the selective, pulsed-laser deposition of hexagonal GaS and monoclinic Ga2S3 films on sapphire substrates from a single Ga 2 S 3 target in high-vacuum conditions. Growth at substrate temperatures below 550 °C causes GaS film formation, which indicates non-stoichiometric transfer from the target to the film. Surprisingly, stoichiometric transfer occurs at substrate temperatures above 650 °C with monoclinic Ga 2 S 3 as the preferred, higher S-content phase. Through a series of growth and annealing experiments, we show that GaS nucleation under S-deficient conditions leads to the preferred growth of this layered, hexagonal phase below 550 °C. Furthermore, GaS films annealed above 650 °C under high vacuum are transformed to Ga 2 S 3 , reflecting the greater stability of the monoclinic phase. By first growing Ga 2 S 3 at a higher temperature and subsequently growing GaS at a lower temperature, we can fabricate GaS/Ga 2 S 3 heterostructures in a single growth process.

36 MATERIALS SCIENCE↗

Structural complexity of γ-Al 2 O 3 : The nature of vacancy ordering and the structure of complex antiphase boundaries

The structure of γ-Al2O3 remains largely undetermined despite decades of research. This is due to the high degree of disorder, which poses significant challenges for structural analysis using conventional crystallographic approaches. Herein, we study the structure of γ-Al2O3 with Scanning Transmission Electron Microscopy (STEM) and ab-initio calculations to provide a complete structural description. We show that the microstructure can be understood in terms of two key structural features of nanoscale spinel domains and finite thickness segments termed as complex antiphase boundaries (cAPB) that provide the domain interconnectivity. The spinel domains have a distinctive preference for vacancy ordering, which can be rationalized in terms of a structure with a stacking disorder. Tetragonal P4 1 2 1 2 or monoclinic P2 1 models, all based on the identical motif, can be considered as representative ordered forms. Individual spinel domains are interconnected via cAPBs, which adopt a distinct non-spinel bonding environment of δ-Al 2 O 3 . The most common cAPB consists of a single delta motif with thickness of just 0.6 nm on (001), with the resulting displacement a/4 [101]. Remarkably, the cAPBs are shown to energetically stabilize the spinel domains of γ-Al 2 O 3 explaining their high abundance. We demonstrate how the tetragonal distortions naturally arise in this intricate microstructure and place the proposed model in the context of phase transformations to high temperature transition aluminas.

36 MATERIALS SCIENCE↗

TRAPPIST-1 Habitable Atmosphere Intercomparison (THAI): motivations and protocol version 1.0

Upcoming telescopes such as the James Webb Space Telescope (JWST), the European Extremely Large Telescope (E-ELT), the Thirty Meter Telescope (TMT) or the Giant Magellan Telescope (GMT) may soon be able to characterize, through transmission, emission or reflection spectroscopy, the atmospheres of rocky exoplanets orbiting nearby M dwarfs. One of the most promising candidates is the late M-dwarf system TRAPPIST-1, which has seven known transiting planets for which transit timing variation (TTV) measurements suggest that they are terrestrial in nature, with a possible enrichment in volatiles. Among these seven planets, TRAPPIST-1e seems to be the most promising candidate to have habitable surface conditions, receiving ∼66 % of the Earth's incident radiation and thus needing only modest greenhouse gas inventories to raise surface temperatures to allow surface liquid water to exist. TRAPPIST-1e is, therefore, one of the prime targets for the JWST atmospheric characterization. In this context, the modeling of its potential atmosphere is an essential step prior to observation. Global climate models (GCMs) offer the most detailed way to simulate planetary atmospheres. However, intrinsic differences exist between GCMs which can lead to different climate prediction and thus observability of gas and/or cloud features in transmission and thermal emission spectra. Such differences should preferably be known prior to observations. In this paper we present a protocol to intercompare planetary GCMs. Four testing cases are considered for TRAPPIST-1e, but the methodology is applicable to other rocky exoplanets in the habitable zone. The four test cases included two land planets composed of modern-Earth and pure-CO2 atmospheres and two aqua planets with the same atmospheric compositions. Currently, there are four participating models (LMDG, ROCKE-3D, ExoCAM, UM); however, this protocol is intended to let other teams participate as well.

Thomas Jean Daniel Fauchez↗

CO 2 Chemisorption Behavior in Conjugated Carbanion-Derived Ionic Liquids via Carboxylic Acid Formation

Superbase-derived task-specific ionic liquids (STSILs) represent one of the most attractive and extensively studied systems in carbon capture via chemisorption, in which the obtained CO 2 uptake capacity has a strong relationship with the basicity of the anions. High energy input in desorption and side reactions caused by the strong basicity of the anions are still unsolved issues. The development of other customized STSILs leveraging an alternative driving force to achieve efficient CO 2 chemisorption/desorption is highly desirable yet challenging. Here, in this work, carbanion-derived STSILs were developed for efficient CO 2 chemisorption via a carboxylic acid formation pathway. The STSIL with the deprotonated malononitrile molecule ([MN]) as the anion exhibited much higher CO 2 uptake capacity than the one derived from 2-methylmalononitrile ([MMN]). Notably, this trend was opposite to their basicity ([MN] < [MMN]). Detailed characterization of the products, supported by density functional theory simulations of spectra and calculations of the reaction energetics, demonstrated that carboxylic acid was formed upon reacting with CO 2 via proton transfer in [MN]-derived STSILs but not in the case of [MMN] due to lack of an α-H. The preference of the carboxylic acid product over carboxylate formation was driven by the extended conjugation among the central sp 2 carbon, the as-formed carboxylic acid, and the two nitrile groups. The achievements made in this work provide an alternative design principle of STSILs by leveraging the extended conjugation in the CO 2 -integrated product.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Liquid Crystalline Thermosets from Ester, Ester-Imide, and Ester-Amide Oligomers

Main chain thermotropic liquid crystal esters, ester-imides, and ester-amides were prepared from AA, BB, and AB type monomeric materials and were end-capped with phenylacetylene, phenylmaleimide, or nadimide reactive end-groups. The resulting reactive end-capped liquid crystal oligomers exhibit a variety of improved and preferred physical properties. The end-capped liquid crystal oligomers are thermotropic and have, preferably, molecular weights in the range of approximately 1000-15,OOO grams per mole. The end-capped liquid crystal oligomers have broad liquid crystalline melting ranges and exhibit high melt stability and very low melt viscosities at accessible temperatures. The end-capped liquid crystal oligomers are stable for up to an hour in the melt phase. These properties make the end-capped liquid crystal oligomers highly processable by a variety of melt process shape forming and blending techniques including film extrusion, fiber spinning, reactive injection molding (RIM), resin transfer molding (RTM), resin film injection (RFI), powder molding, pultrusion, injection molding, blow molding, plasma spraying and thermo-forming. Once processed and shaped, the end- capped liquid crystal oligomers were heated to further polymerize and form liquid crystalline thermosets (LCT). The fully cured products are rubbers above their glass transition temperatures. The resulting thermosets display many properties that are superior to their non-end-capped high molecular weight analogs.

Theodornus J Dingemans↗

An Unusual Transmission Spectrum for the Sub-Saturn KELT-11b Suggestive of a Subsolar Water Abundance

We present an optical-to-infrared transmission spectrum of the inflated sub-Saturn KELT-11b measured with the Transiting Exoplanet Survey Satellite (TESS), the Hubble Space Telescope (HST) Wide Field Camera 3 G141 spectroscopic grism, and the Spitzer Space Telescope (Spitzer) at 3.6 μm, in addition to a Spitzer 4.5 μm secondary eclipse. The precise HST transmission spectrum notably reveals a low-amplitude water feature with an unusual shape. Based on free-retrieval analyses with varying molecular abundances, we find strong evidence for water absorption. Depending on model assumptions, we also find tentative evidence for other absorbers (HCN, TiO, and AlO). The retrieved water abundance is generally ≲0.1× solar (0.001–0.7× solar over a range of model assumptions), several orders of magnitude lower than expected from planet formation models based on the solar system metallicity trend. We also consider chemical-equilibrium and self-consistent 1D radiative-convective equilibrium model fits and find that they, too, prefer low metallicities ([M/H] ≲ -2, consistent with the free-retrieval results). However, all of the retrievals should be interpreted with some caution because they either require additional absorbers that are far out of chemical equilibrium to explain the shape of the spectrum or are simply poor fits to the data. Finally, we find that the Spitzer secondary eclipse is indicative of full heat redistribution from KELT-11b’s dayside to nightside, assuming a clear dayside. These potentially unusual results for KELT-11b’s composition are suggestive of new challenges on the horizon for atmosphere and formation models in the face of increasingly precise measurements of exoplanet spectra.

79 ASTRONOMY AND ASTROPHYSICS↗