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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 523 records · Page 29
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Probing Supercritical Phase Transition using Ultrafast X-ray Diagnostics (Final Technical Report)

Over recent years, several hypotheses have been put forward to elucidate supercritical transition states. Despite significant progress on the fundamental understanding of fluids at these supercritical conditions, important questions concerning the microstructure and dynamical processes remain. A particular research issue is hereby the fundamental understanding of the morphology of the molecular microstructure and its effect on the macroscopic behaviour and thermodynamic response functions. It is widely believed that the supercritical state is homogeneous without structural and dynamic observables to distinguish between a liquid and a vapor. However, recent investigations have identified regions of distinct liquid-like or vapor-like properties even under supercritical conditions. Specifically, it was shown that the transition between liquid-like and vapor-like states occurs across an extension to the coexistence line, marked by almost discontinuous changes in fluid properties. This transition was first identified experimentally by Nishikawa and Tanaka and stands in contrast to the classical presentation of the supercritical state space as a featureless, homogeneous domain. Structurally, the most important properties of supercritical fluids are the dynamic heterogeneities and local density fluctuations that are present within the fluid state at the microscopic level. These inhomogeneities are associated with the formation of molecular clusters of various sizes with liquid-like properties separated by voids of unbound gas-phase molecules which continuously restructure itself at picosecond timescales. By utilizing ultrafast X-ray Photon Correlation Spectroscopy (XPCS) at the Linac Coherent Light Source (LCLS) and X-ray synchrotron measurements as an experimental probe of these structural changes at the molecular level we seek to elucidate the higher-order phase transition from a liquid-like to a vapor-like state in the region extending the critical point. Open questions we seek to address particularly with XPCS are: (i) the underlying mechanisms responsible for the density fluctuations at supercritical conditions and how these dynamical processes at the molecular level affect the thermodynamic response functions and (ii) on what timescales do dynamical processes evolve that are associated with thermalization, molecular diffusion, and intermolecular cluster transfer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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 NTRS1975

Distribution and significance of chromium in meteorites

Chromium is present as a minor element in all meteorite types. Depending on the meteorite type it is lithophile (most frequent), chalcophile (less frequent), or siderophile (rare). Chromium is an indicator of physical and chemical conditions of meteorite formation, especially of the state of oxidation. The Cr contents of meteoritic chromites are related to classification and can be used to distinguish among meteorite types that contain this mineral. The distribution of Cr between coexisting pyroxenes may indicate the degree of equilibration of this mineral pair. Siderophile Cr appears to result from primitive condensation processes rather than secondary reduction processes. The lack of much experimental data on Cr in silicate systems limits the interpretation of the occurrences of Cr-silicate phases, ureyite and krinovite, in the meteorite type in which they occur.

Bunch, T. E.↗
DOE OSTI2025

Carbonation and Sulfidation of Mg- and Ni-Containing Solutions: Implications for Carbon Mineralization and Critical Element Recovery

Carbonation of alkaline earth metals ( e.g. , magnesium (Mg)) and sulfidation of nickel (Ni) are promising methods to achieve concurrent carbon mineralization and selective Ni recovery. However, the coexistence of alkaline earth metals and Ni from silicate ores or mining wastewater complicates the carbonation and sulfidation owing to cation coprecipitation. To better understand simultaneous metal carbonation and Ni-sulfide formation, we used Mg- and Ni-containing solutions and systematically investigated the Mg and Ni coprecipitates’ phase transformation during sequential/concurrent carbonation and sulfidation. During a single carbonation process, hydromagnesite dehydrated and formed magnesite over time. Nickel bicarbonate formed and became a Mg–Ni carbonate solid solution because of their similar ionic radii. During a single sulfidation process, the pH did not affect Ni-sulfide formation, but it controlled Mg behavior. Specifically, at pH 9.6, brucite formed, while at pH 7.8, Mg 2+ remained in the solution. For the sequential carbonation–sulfidation process, Ni-carbonate formed during carbonation converted to Ni-sulfide because of the low Ni-sulfide K sp . For the sulfidation–carbonation process, Ni-sulfide remained the same even after carbonation and Mg-carbonate precipitates. For the concurrent carbonation and sulfidation process, Mg-carbonate and Ni-sulfide formed simultaneously. Finally, this study develops a scientific foundation of carbonation and sulfidation processes, benefiting coupled CO 2 storage and sulfide-enabled resource recovery.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Symmetry breaking forms split-off flat bands in quantum oxides controlling metal versus insulator phases

The crystal structure used as input to electronic structure calculation of conventionally bonded solids consists primarily of the standard crystallographic degrees of freedom. Quantum solids sometimes have additional microscopic degrees of freedom (m-DOF) nested within the crystallographic structure. These might include local motifs including positional (Peierls dimers, deformed octahedra, Jahn-Teller distortions), magnetic (local moment configurations) and dipolar (local ferroelectric configurations). Such motifs can be observed experimentally via local probes that avoid averaging, and theoretically as distinct total energy lowering features relative to more simplified “average crystallographic structures”. Here we examine the ability of electronic structure methods independent of strong correlation physics to explain the broad phenomenology of metal-insulator selectivity in quantum oxides by energy-lowering symmetry breaking. We do this by avoiding the restriction of considering only (i) electron-electron interactions in a fixed unresponsive lattice—as done in Mott strong correlation explanations—allowing, however, (ii) local positional and magnetic motifs that coexist within a crystallographic landscape. We find in a broad range of quantum oxides with different symmetry breaking modes the formation of split-off flat bands that can also control metallic versus insulating characteristics. The split-off band effect is common to magnetic and non-magnetic materials, including both binary and ternary oxides. One finds that when such local symmetry breaking motifs are considered in mean-field-like (e.g. density functional theory) electronic structure calculations of quantum oxides, they explain many of the observed trends in metal vs insulator phases discussed otherwise in prior literature via strong correlation in symmetry unbroken view.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Atomic-scale electronic structure of the cuprate pair density wave state coexisting with superconductivity

In this work, by making a variety of quantitative comparisons between electronic visualization experiments and a theory describing coexisting pair density wave and superconductive states in cuprates, we find striking correspondence throughout. Therefore, our model can explain the microscopic origins of many key atomic-scale phenomena of the cuprate broken-symmetry state. These observations are consistent with the possibility that a short-range pair density wave (PDW) state coexists with superconductivity below a critical hole density in Bi 2 Sr 2 CaCu 2 O 8 , that the charge density wave modulations in cuprates are a consequence of the PDW state, that the cuprate pseudogap is the antinodal gap of the PDW, and that the critical point in the cuprate phase diagram occurs due to disappearance of the PDW.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Colossal transverse magnetoresistance due to nematic superconducting phase fluctuations in a copper oxide

Electronic anisotropy (“nematicity”) has been detected in cuprate superconductors by various experimental techniques. Using angle-resolved transverse resistance (ARTR) measurements, a very sensitive and background-free technique that can detect 0.5% anisotropy in transport, we have observed it also in La 2-x Sr x CuO 4 (LSCO) for 0.02 ≤ x ≤ 0.25. A central enigma in LSCO is the rotation of the nematic director (orientation of the largest longitudinal resistance) with temperature; this has not been seen before in any material. Here, we address this puzzle by measuring the angle-resolved transverse magnetoresistance (ARTMR) in LSCO. We report the discovery of colossal transverse magnetoresistance (CTMR)—an order-of-magnitude drop in the transverse resistivity in the magnetic field of 6 T. We show that the apparent rotation of the nematic director is caused by anisotropic superconducting fluctuations, which are not aligned with the normal electron fluid, consistent with coexisting bond-aligned and diagonal nematic orders. We quantify this by modeling the (magneto-)conductivity as a sum of normal (Drude) and paraconducting (Aslamazov–Larkin) channels but extended to contain anisotropic Drude and Cooper-pair effective mass tensors. Strikingly, the anisotropy of Cooper-pair stiffness is much larger than that of the normal electrons. It grows dramatically on the underdoped side, where the fluctuations become quasi-one-dimensional. Our analysis is general rather than model dependent. Still, we discuss some candidate microscopic models, including coupled strongly-correlated ladders where the transverse (interladder) phase stiffness is low compared with the longitudinal intraladder stiffness, as well as the anisotropic superconducting fluctuations expected close to the transition to a pair-density wave state.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Twofold van Hove singularity and origin of charge order in topological kagome superconductor CsV 3 Sb 5

The layered vanadium antimonides AV 3 Sb 5 (A = K, Rb, Cs) are a recently discovered family of topological kagome metals that exhibit a range of strongly correlated electronic phases including charge order and superconductivity. However, it is not yet understood how the distinctive electronic structure of the kagome lattice is linked to the observed many-body phenomena. Here we combine angle-resolved photoemission spectroscopy and density functional theory to reveal multiple kagome-derived van Hove singularities (vHS) coexisting near the Fermi level of CsV 3 Sb 5 and analyse their contribution to electronic symmetry breaking. The vHS are characterized by two distinct sublattice flavours (p-type and m-type), which originate, respectively, from their pure and mixed sublattice characters. These twofold vHS flavours of the kagome lattice critically determine the pairing symmetry and unconventional ground states emerging in the AV 3 Sb 5 series. We establish that, among the multiple vHS in CsV 3 Sb 5 , the m-type vHS of the d xz /d yz kagome band and the p-type vHS of the d xy /d x2–y2 kagome band are located very close to the Fermi level, setting the stage for electronic symmetry breaking. The former band is characterized by pronounced Fermi surface nesting, while the latter exhibits a higher-order vHS. Furthermore, our work reveals the essential role of kagome-derived vHS for the collective phenomena realized in the AV 3 Sb 5 family.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Dissipative Phase Transition in the Two-Photon Dicke Model

We explore the dissipative phase transition of the two-photon Dicke model, a topic that has garnered significant attention recently. Our analysis reveals that while single-photon loss does not stabilize the intrinsic instability in the model, the inclusion of two-photon loss restores stability, leading to the emergence of superradiant states, which coexist with the normal vacuum states. Using a second-order cumulant expansion for the photons, we derive an analytical description of the system in the thermodynamic limit, which agrees well with the exact calculation results. Additionally, we present the Wigner function for the system, shedding light on the breaking of the 𝑍4 symmetry inherent in the model. These findings offer valuable insights into stabilization mechanisms in open quantum systems and pave the way for exploring complex nonlinear dynamics in two-photon Dicke models.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
NASA NTRS2002

Physics of Hard Sphere Experiment: Scattering, Rheology and Microscopy Study of Colloidal Particles

The Physics of Hard Sphere Experiment has two incarnations: the first as a scattering and rheology experiment on STS-83 and STS-94 and the second as a microscopy experiment to be performed in the future on LMM on the space station. Here we describe some of the quantitative and qualitative results from previous flights on the dynamics of crystallization in microgravity and especially the observed interaction of growing crystallites in the coexistance regime. To clarify rheological measurements we also present ground based experiments on the low shear rate viscosity and diffusion coefficient of several hard sphere experiments at high volume fraction. We also show how these experiments will be performed with confocal microscopy and laser tweezers in our lab and as preparation for the phAse II experiments on LMM. One of the main aims of the microscopy study will be the control of colloidal samples using an array of applied fields with an eye toward colloidal architectures. Temperature gradients, electric field gradients, laser tweezers and a variety of switchable imposed surface patterns are used toward this control.

Z D Cheng↗
NASA NTRS1999

Containerless, Low-Gravity Undercooling of Ti-Ce Alloys in the MSFC Drop Tube

Previous tests of the classical nucleation theory as applied to liquid-liquid gap miscibility systems found a discrepancy between experiment and theory in the ability to undercool one of the liquids before the L1-L2 separation occurs. To model the initial separation process in a two-phase liquid mixture, different theoretical approaches, such as free-energy gradient and density gradient theories, have been put forth. If there is a large enough interaction between the critical liquid and the crucible, both models predict a wetting temperature (T(sub w)) above which the minority liquid perfectly wets and layers the crucible interface, but only on one side of the immiscibility dome. Materials with compositions on the other side of the dome will have simple surface adsorption by the minority liquid before bulk separation occurs when the coexistence (i.e., binoidal) line in reached. If the interaction between the critical liquid and the crucible were to decrease, T(sub w) would increase, eventually approaching the critical consolute temperature (T(sub cc)). If this situation occurs, then there could be large regions of the miscibility gap where non-perfect wetting conditions prevail resulting in droplets of L1 liquid at the surface having a non-zero contact angle. The resulting bulk structure will then depend on what happens on the surface and the subsequent processing conditions. In the past several decades, many experiments in space have been performed on liquid metal binary immiscible systems for the purpose of determining the effects that different crucibles may have on the wetting and separation process of the liquids. Potard performed experiments that showed different crucible materials could cause the majority phase to preferentially wet the container and thus produce a dispersed microstructure of the minority phase. Several other studies have been performed on immiscibles in a semi-container environment using an emulsion technique. Only one previous study was performed using completely containerless processing of immiscible metals and the results of that investigation are similar to some of the emulsion studies. In all the studies, surface wetting was attributed as the cause for the similar microstructures or the asymmetry in the ability to undercool the liquid below the binoidal on one side of the immiscibility dome. By removing the container completely from the separation process, it was proposed that the loss of the crucible/liquid interaction would produce a large shift in T(sub w) and thus change the wetting characteristics at the surface. By investigating various compositions across the miscibility gap, a change in the type and amount of liquid wetting at the surface of a containerless droplet should change the surface nucleating behavior of the droplet - whether it be the liquid-liquid wetting or the liquid-to-solid transition. Undercooling of the liquid into the metastable region should produce significant differences in the separation process and the microstructure upon solidification. In this study, we attempt to measure these transitions by monitoring the temperature of the sample by optical pyrometry. Microstructural analysis will be made to correlate with the degree of undercooling and the separation mechanisms involved.

Robinson, M. B.↗
DOE OSTI2023

Ab initio structural dynamics of pure and nitrogen-containing amorphous carbon

Abstract Amorphous carbon (a-C) has attracted considerable interest due to its desirable properties, which are strongly dependent on its structure, density and impurities. Using ab initio molecular dynamics simulations we show that the sp 2 /sp 3 content and underlying structural order of a-C produced via liquid quenching evolve at high temperatures and pressures on sub-nanosecond timescales. Graphite-like densities ( $$\lesssim$$ ≲ 2.7 g/cc) favor the formation of layered arrangements characterized by sp 2 disordered bonding resembling recently synthesized monolayer amorphous carbon (MAC), while at diamond-like densities ( $$\gtrsim$$ ≳ 3.3 g/cc) the resulting structures are dominated by disordered tetrahedral sp 3 hybridization typical of diamond-like amorphous carbon (DLC). At intermediate densities the system is a highly compressible mixture of coexisting sp 2 and sp 3 regions that continue to segregate over 10’s of picoseconds. The addition of nitrogen (20.3%) (a-CN) generates major system features similar with those of a-C, but has the unexpected effect of reinforcing the thermodynamically disfavored carbon structural motifs at low and high densities, while inhibiting phase separation in the intermediate region. At the same time, no nitrogen elimination from the carbon framework is observed above $$\simeq$$ ≃ 2.8 g/cc, suggesting that nitrogen impurities are likely to remain embedded in the carbon structures during fast temperature quenches at high pressures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

NMR study of Ni 50+x ⁢Ti 50-x strain glasses

Here, we studied Ni 50+x ⁢Ti 50-x with compositions up to x = 2, performing 47 Ti and 49 Ti nuclear magnetic resonance (NMR) measurements from 4 to 400 K. For large x in this system, a strain glass appears in which frozen ferroelastic nanodomains replace the displacive martensite structural transition. Here, we demonstrate that NMR can provide an extremely effective probe of the strain-glass freezing process, with large changes in NMR line shape due to the effects of random strains which become motionally narrowed at high temperatures. At the same time with high-resolution x-ray diffraction we confirm the lack of structural changes in x ≥ 1.2 samples, while we show that there is little change in the electronic behavior across the strain-glass freezing temperature. NMR spin-lattice relaxation time (T 1 ) measurements provide a further measure of the dynamics of the freezing process, and indicate a predominantly thermally activated behavior both above and below the strain-glass freezing temperature. We show that the strain-glass results are consistent with a very small density of critically divergent domains undergoing a Vogel-Fulcher-type freezing process, coexisting with domains exhibiting faster dynamics and stronger pinning.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Strong and fragile topological Dirac semimetals with higher-order Fermi arcs

Abstract Dirac and Weyl semimetals both exhibit arc-like surface states. However, whereas the surface Fermi arcs in Weyl semimetals are topological consequences of the Weyl points themselves, the surface Fermi arcs in Dirac semimetals are not directly related to the bulk Dirac points, raising the question of whether there exists a topological bulk-boundary correspondence for Dirac semimetals. In this work, we discover that strong and fragile topological Dirac semimetals exhibit one-dimensional (1D) higher-order hinge Fermi arcs (HOFAs) as universal, direct consequences of their bulk 3D Dirac points. To predict HOFAs coexisting with topological surface states in solid-state Dirac semimetals, we introduce and layer a spinful model of an s – d -hybridized quadrupole insulator (QI). We develop a rigorous nested Jackiw–Rebbi formulation of QIs and HOFA states. Employing ab initio calculations, we demonstrate HOFAs in both the room- ( α ) and intermediate-temperature ( α ″ ) phases of Cd 3 As 2 , KMgBi, and rutile-structure ( $$ \beta ^{\prime} $$ β ′ -) PtO 2 .

Science & Technology - Other Topics↗
DOE OSTI2020

Dynamical Bonding Driving Mixed Valency in a Metal Boride

Abstract Samarium hexaboride is an anomaly, having many exotic and seemingly mutually incompatible properties. It was proposed to be a mixed‐valent semiconductor, and later a topological Kondo insulator, and yet has a Fermi surface despite being an insulator. We propose a new and unified understanding of SmB 6 centered on the hitherto unrecognized dynamical bonding effect: the coexistence of two Sm−B bonding modes within SmB 6 , corresponding to different oxidation states of the Sm. The mixed valency arises in SmB 6 from thermal population of these distinct minima enabled by motion of B. Our model simultaneously explains the thermal valence fluctuations, appearance of magnetic Fermi surface, excess entropy at low temperatures, pressure‐induced phase transitions, and related features in Raman spectra and their unexpected dependence on temperature and boron isotope.

Robinson, Paul J.↗
DOE OSTI2020

Dynamical Bonding Driving Mixed Valency in a Metal Boride

Samarium hexaboride is an anomaly, having many exotic and seemingly mutually incompatible properties. It was proposed to be a mixed-valent semiconductor, and later a topological Kondo insulator, and yet has a Fermi surface despite being an insulator. We propose a new and unified understanding of SmB6 centered on the hitherto unrecognized dynamical bonding effect: the coexistence of two Sm-B bonding modes within SmB6, corresponding to different oxidation states of the Sm. The mixed valency arises in SmB6 from thermal population of these distinct minima enabled by motion of B. Our model simultaneously explains the thermal valence fluctuations, appearance of magnetic Fermi surface, excess entropy at low temperatures, pressure-induced phase transitions, and related features in Raman spectra and their unexpected dependence on temperature and boron isotope.

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

Deterministic chaos in the self-assembly of β sheet nanotubes from an amphipathic oligopeptide

The self-assembly of designed peptides into filaments and other higher-order structures has been the focus of intense interest because of the potential for creating new biomaterials and biomedical devices. These peptide assemblies have also been used as models for understanding biological processes, such as the pathological formation of amyloid. Here we investigate the assembly of an octapeptide sequence, Ac-FKFEFKFE-NH2, motivated by prior studies that demonstrated that this amphipathic beta strand peptide self-assembled into fibrils and biocompatible hydrogels. Using high-resolution cryoelectron microscopy (cryo-EM), we are able to determine the atomic structure for two different coexisting forms of the fibrils, containing four and five beta sandwich protofilaments, respectively. Surprisingly, the inner walls in both forms are parallel beta sheets, while the outer walls are antiparallel beta sheets. Our results demonstrate the chaotic nature of peptide self-assembly and illustrate the importance of cryo-EM structural analysis to understand the complex phase behavior of these materials at near-atomic resolution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Molecular Structure of Adsorbed Water Phases in Silica Nanopores

The adsorption of water vapor in silica nanopores with different pore morphologies and surface hydrophilicities was studied to quantify the densities and thicknesses of the water sorption layers and deduce their molecular structures. Water adsorption to surface hydroxyls is described by a multilayer sorption model. At low pressure, the water adsorption isotherms are largely independent of pore size and the adsorbed amounts scale with the surface hydroxyl density. Adsorbed-phase densities corresponding to the adsorption of two water molecules per surface hydroxyl group are found in the first adsorbed water layer for a wide range of surface hydroxyl densities. The densities and layer thickness values found in narrow pores indicate that patchy adsorbed layers form if not enough water molecules exist for a full layer, which coexist with dry pore surface regions. This behavior indicates cooperative adsorption effects, i.e., a preference for the formation of hydrogen bonds between water molecules bound to surface hydroxyls. In narrow pores, pore condensation limits further growth of the sorption layer, and in larger pores and at the planar quartz surface, a second adsorbed water layer is formed, which can hold up to approximately 4 additional water molecules per surface hydroxyl group. The water molecules in these thicker adsorption layers arrange such that the sorption layer density is similar to the bulk water density. Pore confinement limitations on the sorption layers are observed in pores with radii of as large as 8 nm. Molecular dynamics modeling reveals two preferential orientations for water molecules adsorbing to surface hydroxyl groups and suggests an intralayer structuring in the adsorbed monolayer. Furthermore, adsorbed water molecules in the sorption layer are bonded to the surface hydroxyl group via the donation and acceptance of hydrogen bonds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗