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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 703 records · Page 39
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Probing Metastable Domain Dynamics via Automated Experimentation in Piezoresponse Force Microscopy

The dynamics of complex topological defects in ferroelectric materials is explored using automated experimentation in piezoresponse force microscopy. Specifically, a complex trigger system (i.e., “FerroBot”) is employed to study metastable domain-wall dynamics in Pb 0.6 Sr 0.4 TiO 3 thin films. Several regimes of superdomain wall dynamics have been identified, including smooth domain-wall motion and significant reconfiguration of the domain structures. We have further demonstrated that microscopic mechanisms of the domain-wall dynamics can be identified; i.e., domain-wall bending can be separated from irreversible domain reconfiguration regimes. In conjunction, phase-field modeling was used to corroborate the observed mechanisms. As such, the observed superdomain dynamics can provide a model system for classical ferroelectric dynamics, much like how colloidal crystals provide a model system for atomic and molecular systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Optical Control of Adaptive Nanoscale Domain Networks

Adaptive networks can sense and adjust to dynamic environments to optimize their performance. Understanding their nanoscale responses to external stimuli is essential for applications in nanodevices and neuromorphic computing. However, it is challenging to image such responses on the nanoscale with crystallographic sensitivity. Here, the evolution of nanodomain networks in (PbTiO 3 ) n /(SrTiO 3 ) n superlattices (SLs) is directly visualized in real space as the system adapts to ultrafast repetitive optical excitations that emulate controlled neural inputs. The adaptive response allows the system to explore a wealth of metastable states that are previously inaccessible. Their reconfiguration and competition are quantitatively measured by scanning x-ray nanodiffraction as a function of the number of applied pulses, in which crystallographic characteristics are quantitatively assessed by assorted diffraction patterns using unsupervised machine-learning methods. The corresponding domain boundaries and their connectivity are drastically altered by light, holding promise for light-programable nanocircuits in analogy to neuroplasticity. Phase-field simulations elucidate that the reconfiguration of the domain networks is a result of the interplay between photocarriers and transient lattice temperature. The demonstrated optical control scheme and the uncovered nanoscopic insights open opportunities for the remote control of adaptive nanoscale domain networks.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Crystallization of a Neptunyl Oxalate Hydrate from Solutions Containing Np V and the Uranyl Peroxide Nanocluster U 60 Ox 30

Uranyl peroxide nanoclusters are an evolving family of materials with potential applications throughout the nuclear fuel cycle. While several studies have investigated their interactions with alkali and alkaline earth metals, no studies have probed their interactions with the actinide elements. This work describes a system containing U 60 Ox 30 , [((UO 2 )(O 2 )) 60 (C 2 O 4 ) 30 ] 60- , and neptunium(V) as a function of neptunium concentration. Ultra-small and small angle X-ray scattering were used to observe these interactions in the aqueous phase, and X-ray diffraction was used to observe solid products. The results show that neptunium induces aggregation of U 60 Ox 30 when the neptunium concentration is ≤ 10 mM, whereas (NpO 2 ) 2 C 2 O 4 ·6H 2 O(cr) and studtite ultimately form at 15–25 mM neptunium. Finally, the latter result suggests that neptunium coordinates with the bridging oxalate ligands in U 60 Ox 30 , leaving metastable uranyl peroxide species in solution, and is an important finding given the potential application of uranyl peroxide nanoclusters in the recycling of used nuclear fuel.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
NASA NTRS1991

The use of containerless processing in researching reactive materials

It has recently become possible to perform containerless, high-temperature liquid-phase processing of many nonvolatile materials without resort to orbital microgravity, thereby facilitating the conduct of materials research in conjunction with noncontact diagnostic instruments. The melt-levitation techniques are electromagnetic, aerodynamic, acoustic, aeroacoustic, and electrostatic; nonorbital microgravity conditions are obtainable aboard NASA's KC-135 aircraft on parabolic flight paths, as well as in drop tubes and towers. Applications encompass the purification of metals and the creation of nonequilibrium and metastable structures. Process control and property measurements include optical pyrometry and emissivity, laser polarimetry, and drop calorimetry.

Weber, J. K. R.↗
DOE OSTI2021

Imaging the short-lived hydroxyl-hydronium pair in ionized liquid water

The radiolysis of water is ubiquitous in nature and plays a critical role in numerous biochemical and technological applications. Although the elementary reaction pathways for the ionized water have been studied, the short-lived intermediate complex and structural dynamic response after the proton transfer reaction remain poorly understood. Here, using liquid-phase ultrafast electron diffraction technique to measure the intermolecular O··O and O··H bonds, we captured the short-lived radical-cation complex OH(H 3 O + ) that was formed within 140 femtoseconds through a direct oxygen-oxygen bond contraction and proton transfer, followed by the radical-cation pair dissociation and the subsequent structural relaxation of water within 250 femtoseconds. These measurements provide direct evidence of capturing this metastable radical-cation complex before separation, thereby improving our fundamental understanding of elementary reaction dynamics in ionized liquid water.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1989

Ginzburg-Landau theory for the solid-liquid interface of bcc elements. II - Application to the classical one-component plasma, the Wigner crystal, and He-4

The previously developed Ginzburg-Landau theory for calculating the crystal-melt interfacial tension of bcc elements to treat the classical one-component plasma (OCP), the charged fermion system, and the Bose crystal. For the OCP, a direct application of the theory of Shih et al. (1987) yields for the surface tension 0.0012(Z-squared e-squared/a-cubed), where Ze is the ionic charge and a is the radius of the ionic sphere. Bose crystal-melt interface is treated by a quantum extension of the classical density-functional theory, using the Feynman formalism to estimate the relevant correlation functions. The theory is applied to the metastable He-4 solid-superfluid interface at T = 0, with a resulting surface tension of 0.085 erg/sq cm, in reasonable agreement with the value extrapolated from the measured surface tension of the bcc solid in the range 1.46-1.76 K. These results suggest that the density-functional approach is a satisfactory mean-field theory for estimating the equilibrium properties of liquid-solid interfaces, given knowledge of the uniform phases.

Zeng, X. C.↗
NASA NTRS1991

Laboratory and field studies of stratospheric aerosols: Phase changes under high supersaturation

It is well known that water in the form of isolated small droplets supercool as much as 40 C below their equilibrium melting point. Solutions similarly supercool (with respect to water) and supersaturate (with respect of the solute). Experiments are described in which bulk solutions typical of atmospheric aerosols (nitric acid, sulfuric acid, and hydrates; ammonium sulfate; ammonium bisulfate; sodium chloride) are supercooled and/or supersaturated and nucleated to initiate crystal growth. Supersaturation of 300 percent is readily attainable, with linear growth of crystals increasing roughly as (supercooling/supersaturation)sup 2. The implication of the experiments is that the situation of metastability in polar stratosphere clouds is very likely, with nucleation only occuring under a high degree of supercooling or supersaturation.

Hallet, John↗
DOE OSTI2022

Phase II testing of Xenon International on Mount Schauinsland, Germany

Station RN33 on Mount Schauinsland near Freiburg, Germany, is part of the International Monitoring System monitoring radioxenon in air ( 131m Xe, 133 Xe, 133m Xe, and 135 Xe) for verification of the Comprehensive Nuclear Test Ban Treaty. Here, we present data from phase II testing of a new system, Xenon International at RN33, July 14th, 2021 to Jan 22nd, 2022, together with SPALAX data from the same time period. Radioxenon could be detected in 473 of 719 samples, among them many multiple isotope detections. Activity concentrations of spiked and selected environmental samples were verified by laboratory reanalysis. Finally, the sensitivity of Xenon International for radioxenons is up to one order of magnitude better for the metastable isotopes than that of the SPALAX, with a shorter sampling duration of 6 h.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗
DOE OSTI2021

Pressurized in situ X-ray diffraction insights into super/subcritical carbonation reaction pathways of steelmaking slags and constituent silicate minerals

This study explores mineral carbonation of industrial stainless steelmaking slags and relevant synthetic constituent minerals via in situ pressurized X-ray diffraction, to clarify carbonation reaction pathways and efficiency for carbon storage and waste valorization. The primary mineral phases of Argon Oxygen Decarburization (AOD) and Continuous Casting (CC) slags, namely, åkermanite, bredigite, cuspidine, merwinite, and β- and γ-C 2 S, were reacted in a custom-built beryllium-capped XRD reactor filled with either water-saturated (wet) subcritical CO 2 (g), or wet supercritical CO 2(SC) , in a series of carbonation experiments. Formation of calcite and aragonite was observed for most Ca-bearing minerals, transient precipitation of metastable vaterite was observed, while carbonation of AOD and CC slags in CO 2(SC) resulted in hydrated crystalline calcium carbonates and indirect evidence of amorphous carbonate. Overall, results obtained suggest that low-pressure subcritical carbonation routes are attractive for standalone slag carbonation processes, while high-pressure supercritical carbonation routes are amiable to symbiotic integration with CO 2(SC) -generating green technologies.

42 ENGINEERING↗
NASA NTRS1993

Micrometeorite dynamic pyrometamorphism: Nonstoichiometric clinoenstatite (CLEN)

Polymorphs of enstatite are common phases in many meteorites. They contain clues on their formation and the thermal evolution of their host rock which includes shock metamorphism. Rare, micron-sized, CLEN whiskers and thin platelets in chondritic porous micrometeorites were interpreted as solar nebula condensates that remained unaffected during atmospheric entry flash-heating. This CLEN formed by protoenstatite (PEN) inversion whereby the surface energy of the micron-sized PEN crystals aided the OREN-CLEN transformation or by metastable growth. Ca-poor, Mg,Fe-pyroxene with unequilibrated, intraparticle, Mg/(Mg+Fe) distributions occur in most chondritic micrometeorites. These distributions are a parent body signature that survived dynamic pyrometamorphism because the duration of the thermal spike during atmospheric entry is too short but this conclusion does not consider the ultrafine grain size of micrometeorites. The maximum temperature and duration of the heating event will depend on the kinetic energy and entry angle of the incoming micrometeorite. But lacking detailed petrological data for an individual particle, its thermal profile during atmospheric entry can not be deduced from its mass alone as a function of entry angle. In order to constrain dynamic pyrometamorphism in unmelted micrometeorites, I determined the petrological composition and silicate mineralogy in non-chondritic micrometeorites L2005T13, L2005E40, and L2006A28.

Rietmeijer, Frans J. M.↗
DOE OSTI2023

The hydration, microstructure, and mechanical properties of vaterite calcined clay cement (VC 3 )

Limestone (calcite) calcined clay cement (LC 3 ) is a promising low-CO 2 binder, but the low activity of calcite cannot compensate the reduction in clinker factor, resulting in low one-day strength and limiting its broad applications. As recent carbon capture and utilization technologies allow scalable production of vaterite, a more reactive CaCO 3 polymorph, we overcome the challenge by introducing vaterite calcined clay cement (VC 3 ), inspired by the vaterite-calcite phase change. In the present study, VC 3 exhibits higher compressive strengths and faster hydration than LC 3 . Compared to hydrated LC 3 , hydrated VC 3 exhibits increased amount of hemi- and mono-carboaluminate formation and decreased amount of strätlingite formation. With gypsum adjustment, the 1-day strength of VC 3 is higher than that of pure cement reference. Finally, VC 3 , a low-CO 2 binder, presents great potential as a host of the metastable CaCO 3 for carbon storage and utilization and as an enabler of carbon capture at gigaton scales.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Computational investigation of hysteresis and phase equilibria of n-alkanes in a metal-organic framework with both micropores and mesopores

Abstract Adsorption hysteresis is a phenomenon related to phase transitions that can impact applications such as gas storage and separations in porous materials. Computational approaches can greatly facilitate the understanding of phase transitions and phase equilibria in porous materials. In this work, adsorption isotherms for methane, ethane, propane, and n-hexane were calculated from atomistic grand canonical Monte Carlo (GCMC) simulations in a metal-organic framework having both micropores and mesopores to better understand hysteresis and phase equilibria between connected pores of different size and the external bulk fluid. At low temperatures, the calculated isotherms exhibit sharp steps accompanied by hysteresis. As a complementary simulation method, canonical (NVT) ensemble simulations with Widom test particle insertions are demonstrated to provide additional information about these systems. The NVT+Widom simulations provide the full van der Waals loop associated with the sharp steps and hysteresis, including the locations of the spinodal points and points within the metastable and unstable regions that are inaccessible to GCMC simulations. The simulations provide molecular-level insight into pore filling and equilibria between high- and low-density states within individual pores. The effect of framework flexibility on adsorption hysteresis is also investigated for methane in IRMOF-1.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Out-of-equilibrium processes in crystallization of organic-inorganic perovskites during spin coating

Complex phenomena are prevalent during the formation of materials, which affect their processing-structure-function relationships. Thin films of methylammonium lead iodide (CH 3 NH 3 PbI 3 , MAPI) are processed by spin coating, antisolvent drop, and annealing of colloidal precursors. The structure and properties of transient and stable phases formed during the process are reported, and the mechanistic insights of the underlying transitions are revealed by combining in situ data from grazing-incidence wide-angle X-ray scattering and photoluminescence spectroscopy. Here, we report the detailed insights on the embryonic stages of organic-inorganic perovskite formation. The physicochemical evolution during the conversion proceeds in four steps: i) An instant nucleation of polydisperse MAPI nanocrystals on antisolvent drop, ii) the instantaneous partial conversion of metastable nanocrystals into orthorhombic solvent-complex by cluster coalescence, iii) the thermal decomposition (dissolution) of the stable solvent-complex into plumboiodide fragments upon evaporation of solvent from the complex and iv) the formation (recrystallization) of cubic MAPI crystals in thin film.

36 MATERIALS SCIENCE↗
NASA NTRS1975

Maximum two-phase flow rates of subcooled nitrogen through a sharp-edged orifice

Data are presented of an experiment in which subcooled liquid nitrogen was discharged through a sharp-edged orifice at flow rates near the maximum. The data covered a range of inlet stagnation pressures from slightly above saturation to twice the thermodynamic critical pressure. The data were taken along five separate inlet stagnation isotherms ranging from 0.75 to 1.035 times the thermodynamic critical temperature. The results indicate that subcooled liquids do not choke or approach maximum flow in an asymptotic manner even though the back pressure is well below saturation; and orifice flow coefficients are not constant as is frequently assumed. A metastable jet appears to exist which breaks down if the difference between back pressure and saturation pressure is large enough.

Simoneau, R. J.↗
DOE OSTI2021

Understanding the Reactions Between Fe and Se Binary Diffusion Couples

Spurred by recent discoveries of high-temperature superconductivity in Fe-Se based materials, the magnetic, electronic, and catalytic properties of iron-chalcogenides have drawn significant attention. Furthermore, much remains to be understood about the sequence of phase formation in these systems. In this work, we shed light on this issue by preparing a series of binary Fe-Se ultrathin diffusion couples via designed thin film precursors and investigating their structural evolution as a function of composition and annealing temperature. Two previously unreported Fe-Se phases crystallized during the deposition process on a nominally room-temperature Si substrate in the 27-33% and 37-47% Fe (atomic percent) composition regimes. Both phases completely decompose after annealing to 200°C in a nitrogen glovebox. At higher temperatures, the sequence of phase formation is governed by Se loss in the annealing process, consistent with what would be expected from the phase diagram. Films rich in Fe (53-59% Fe) crystalized during deposition as β-FeSe (P4/nmm) with preferred c-axis orientation to the amorphous SiO 2 substrate surface, providing a means to non-epitaxial self-assembly of crystallographically aligned, iron-rich β-FeSe for future research. Our findings suggest the crystallization of binary Fe-Se compounds at room temperature via near diffusionless transformations should be a significant consideration in future attempts to prepare metastable ternary and higher order compounds containing Fe and Se.

36 MATERIALS SCIENCE↗
NASA NTRS1975

Maximum two-phase flow rates of subcooled nitrogen through a sharp-edged orifice

An experiment was conducted and data are presented in which subcooled liquid nitrogen was discharged through a sharp-edged orifice at flow rates near the maximum. The data covered a range of inlet stagnation pressure from slightly above saturation to twice the thermodynamic critical pressure. The data were taken along five separate inlet stagnation isotherms ranging from 0.75 to 1.035 times the thermodynamic critical temperature. The results indicate that: (1) subcooled liquids do not choke or approach maximum flow in an asymptotic manner even though the back pressure is well below saturation; (2) orifice flow coefficients are not constant as is frequently assumed. A metastable jet appears to exist which breaks down if the difference between back pressure and saturation pressure is large enough.

Simoneau, R. J.↗
NASA NTRS1982

Solidification mechanism of highly undercooled metal alloys

Experiments were conducted on metal droplet undercooling, using Sn-25wt%Pb and Ni-34wt%Sn alloys. To achieve the high degree of undercooling, emulsification treatments were employed. Results show the fraction of supersaturated primary phase is a function of the amount of undercooling, as is the fineness of the structures. The solidification behavior of the tin-lead droplets during recalescence was analyzed using three different hypotheses; (1) solid forming throughout recalescence is of the maximum thermodynamically stable composition; (2) partitionless solidification below the T sub o temperature, and solid forming thereafter is of the maximum thermodynamically stable composition; and (3) partitionless solidification below the T sub o temperature with solid forming thereafter that is of the maximum thermodynamically metastable composition that is possible. The T sub o temperature is calculated from the equal molar free energies of the liquid solid using the regular solution approximation.

Shiohara, Y.↗
DOE OSTI2022

Layered supramolecular hydrogels from thioglycosides

Low molecular weight hydrogels are made of small molecules that aggregate via noncovalent interactions. Here, comprehensive characterization of the physical and chemical properties of hydrogels made from thioglycolipids of the disaccharides lactose and cellobiose with simple alkyl chains is reported. While thiolactoside hydrogels are robust, thiocellobioside gels are metastable, precipitating over time into fibrous crystals that can be entangled to create pseudo-hydrogels. Rheology confirms the viscoelastic solid nature of these hydrogels with storage moduli ranging from 10–600 kPa. Additionally, thiolactoside hydrogels are thixotropic which is a desirable property for many potential applications. Freeze-fracture electron microscopy of xerogels shows layers of stacked sheets that are entangled into networks. These structures are unique compared to the fibers or ribbons typically reported for hydrogels. Differential scanning calorimetry provides gel-to-liquid phase transition temperatures ranging from 30 to 80 °C. Prodan fluorescence spectroscopy allows assignment of phase transitions in the gels and other lyotropic phases of high concentration samples. Phase diagrams are estimated for all hydrogels at 1–10 wt% from 5 to ≥ 80 °C. In conclusion, these hydrogels represent a series of interesting materials with unique properties that make them attractive for numerous potential applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗