Search NASA⌕ Search

SEARCH · Search NASA

Results for “metastable phases”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Additive Molar Volumes in Amorphous Ca/Sr Carbonate Solid Solutions

The development of predictive models of minor element incorporation in crystalline carbonate end products requires an understanding of the fundamental controls on metastable intermediate phase composition. In this study, we used small-angle X-ray scattering (SAXS), X-ray pair distribution function (PDF), thermogravimetric analysis (TGA), inductively coupled plasma mass spectrometry (ICP-MS), and transmission electron microscopy (TEM) to determine the composition-dependent density of an amorphous calcium–strontium carbonate (ACSC) solid solution. The amorphous calcium carbonate (ACC) and strontium carbonate (ASC) measured densities were ρ ACC = 2.19 ± 0.04 g/cm 3 and ρ ASC = 2.97 ± 0.05 g/cm 3 . Throughout our work, the experiments showed a dependence of the water content of the amorphous solid solution on the Sr mole fraction. An equation that relates the molar volume to the average cation radius, the carbonate ion radius, and the water volume was parameterized for hydrated crystalline carbonates and predicted well the molar volume of the ACSC solid solution. This finding indicates that, as for hydrated crystalline carbonates, the molar volumes of amorphous carbonates are additive and that water is a structural component of ACSC. Ab initio molecular dynamics (AIMD) simulations of the ACSC solid solutions showed strong linear correlations between calculated molar volumes and Sr and H 2 O contents, thus supporting the experimental results. In conclusion, our findings highlight the need to consider the full CaCO 3 –MeCO 3 –H 2 O ternary when quantifying metal cation incorporation in ACC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

High-fidelity topochemical polymerization in single crystals, polycrystals, and solution aggregates

Topochemical polymerization (TCP) emerges as a leading approach for synthesizing single crystalline polymers, but is traditionally restricted to transformations in solid-medium. The complexity in achieving single-crystal-to-single-crystal (SCSC) transformations due to lattice disparities and the untapped potential of performing TCP in a liquid medium with solid-state structural fidelity present unsolved challenges. Herein, by using X-rays as the primary means to overcome crystal disintegration, we reveal the details of SCSC transformation during the TCP of chiral azaquinodimethane (AQM) monomers through in situ crystallographic analysis while spotlighting a rare metastable crystalline phase. Complementary in situ investigations of powders and thin films provide critical insights into the side-chain dependent polymerization kinetics of solid-state reactions. Furthermore, we enable TCP of AQM monomers in a liquid medium via an antisolvent-reinforced aggregated state, yielding polymer nanofibers with high crystallinity akin to that of solid-state. This study testifies high structural precision of TCP performed in different states and media, offering critical insights into the synthesis of processable nanostructured polymers with desired structural integrity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Unraveling the origin of air-stability in single-crystalline layered oxide positive electrode materials

Single-crystalline Ni-rich layered oxides present compelling advantages over conventional polycrystalline counterparts toward large-scale applications, including enhanced mechanical stability and higher energy density. Nevertheless, the deleterious effects of air exposure, which is inevitable in industrial processing, on their structure and electrochemical performance remain poorly understood. Herein, we reveal that air exposure is more detrimental to the electrochemical performance of single-crystalline layered oxide positive electrodes than polycrystalline counterparts. It is found that air-induced surface structural distortions are primarily responsible for the electrochemical performance decay of single-crystalline samples rather than the generally believed surface residual lithium. Leveraging multiscale diffraction and imaging techniques, we identify an undesirable structural transition to a metastable O1* phase, which introduces substantial lattice defects and localized strain concentrations within the layered structure. These adverse structural evolutions compromise structural integrity and promote crack initiation during electrochemical cycling, ultimately accelerating capacity fade. Our findings provide critical insights into the air-induced degradation mechanisms and emphasize the urgent need for developing effective stabilization strategies to facilitate the commercial implementation of single-crystalline Ni-rich positive electrodes.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Experimental observations of large changes in electron density distributions in β - Ge

We report the electron density distributions in β-Ge have been experimentally determined at in situ high-pressure conditions using synchrotron diffraction techniques in a diamond anvil cell. Upon decompression, the electron density along the $c$ axis in tetragonal β-Ge displays a sudden drop at 10–11 GPa close to that of the structural α-β transition, while the β-Ge samples remain as single crystals until transforming to metastable Ge phases around 6.7–8.5 GPa. In contrast to the covalently bonded α-Ge that displays only a weak participation of $d$ electrons in the valence band under compression above 7.7 GPa, our experimental results suggest that a large change in $d$-orbital participation can occur in the β-Ge lattice which has mixed covalent and metallic bonding. The β-Ge below 10 GPa may display large fluctuations in electronic properties, which sheds light for exploring novel materials with intriguing electronic and optical properties.

36 MATERIALS SCIENCE↗
DOE OSTI2020

High oxygen pressure floating zone growth and crystal structure of the metallic nickelates R4Ni3O10 ( R=La,Pr )

Single crystals of the metallic Ruddlesden-Popper trilayer nickelates R 4 Ni 3 O 10 ( R = La , Pr ) were successfully grown using an optical-image floating zone furnace under oxygen pressure ( p O 2 ) of 20 bar for La 4 Ni 3 O 10 and 140 bar for Pr 4 Ni 3 O 10 . Furthermore, a combination of synchrotron and laboratory x-ray single-crystal diffraction, high-resolution synchrotron x-ray powder diffraction and measurements of physical properties revealed that R 4 Ni 3 O 10 ( R = La , Pr ) crystallizes in the monoclinic P 2 1 / a ( Z = 2 ) space group at room temperature, and that a metastable orthorhombic phase ( Bmab ) can be trapped by postgrowth rapid cooling. Both La 4 Ni 3 O 10 and Pr 4 Ni 3 O 10 crystals undergo a metal-to-metal transition (MMT) below room temperature. In the case of Pr 4 Ni 3 O 10 , the MMT is found at 157.6 K. For La 4 Ni 3 O 10 , the MMT depends on the lattice symmetry: 147.5 K for Bmab vs 138.6 K for P 2 1 / a . Lattice anomalies were found at the MMT that, when considered together with the pronounced dependence of the transition temperature on subtle structural differences between Bmab and P 2 1 / a phases, demonstrate a not insignificant coupling between electronic and lattice degrees of freedom in these trilayer nickelates.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Dynamics of the metastable st12 to diamond-cubic transition in germanium characterized by neutron spectroscopy

Data related to the manuscript "Dynamics of the metastable st12 to diamond-cubic transition in germanium characterized by neutron spectroscopy". It includes density of states results for st12-Ge, dc-Ge, amorphous-Ge, and the relaxation of st12-Ge to dc-Ge. It also includes diffractions results for the same relaxation experiment. The experiment was performed on the ARCS spectrometer at the SNS. See the Readme.md file in the data set for more information.

36 MATERIALS SCIENCE↗
NASA NTRS1967

Surface-spike growth on NiBr sub 2 crystals - A VLS mode of crystal growth.

Droplets associated with surface-spike growth of crystals of NiBr 2 by sublimation have been analyzed and found to contain Cu, Co, Mn, and Fe in addition to Ni and Br. These elements exist in the bulk of the original charge material in concentrations that are several orders of magnitude lower than that in the droplets. During crystal growth by sublimation the impurities collect on the surface of growing crystals, until sufficient concentrations are reached to cause the nucleation of a metastable liquid phase droplet. Once the liquid phase droplets have been nucleated, they may then become attached to growth steps and produce accelerated growth from these sites. Such processes occur in NiBr 2 , during growth by sublimation, at approximately 500 °C below the melting point of NiBr 2 .

Edward N Sickafus↗
NASA NTRS1980

SPAR and ASTP studies of plane-front solidification and magnetic properties of Bi/MnBi

Eutectic and off-eutectic Bi/MnBi compositions have been directionally solidified parallel, anti-parallel and perpendicular to the gravity vector in a one-g environment and in low-gravity during the ASTP flight. MnBi rod diameter and interparticle spacing distributions are similar for all gravity vector orientations when grown at high solidification rates in one-g. Previously reported ASTP results are explained by the existence of a metastable magnetic phase and off-eutectic solidification models.

Pirich, R. G.↗
NASA NTRS1982

Physicochemical investigation of NiAl with small molybdenum additions

Specimens of four cast NiAl alloys, three of them containing 0.5, 1.0 and 1.5 at. % Mo., were homogenized for 10, 10, and 140 hr at 1373, 1523 and 1273 K, respectively, then kept at 1073, 1173 and 1323 K for 60, 120 and 3 hr, respectively, and quenched in icy water. The precipitation of a metastable Ni3Mo phase was observed at temperatures between 1073 and 1523 K. Molybdenum substituted for nickel was found to inhibit the lattice disordering in NiAl at 1073 and 1523 K.

Troshkina, V. A.↗
NASA NTRS1986

The evolution and growth of Al2O3 scales on beta-NiAl

The formation and growth of Al2O3 scales on (beta)-NiAl were studied using electron microscopy and other analytical techniques to gain an understanding of the oxidation properties of (beta)-NiAl and of alumina-forming alloys, in general. The transient and mature stages of oxidation were studied as well as the transformation stage during which the oxide scale transforms from metastable Al2O3 phases to the thermodynamically stable alpha-Al2O3 phase. The transient oxidation stages were studied at 800 deg C and for short times at 1100C. At 800C, the scales consist predominantly of delta-Al2O3 which forms by cation vacancy ordering in the defective spinel lattice of gamma-Al2O3. At 1100C, a fast-growth morphology of theta-Al2O3 forms as a surface layer over delta-Al2O3. For both oxidation temperatures, the scales are often epitaxially oriented with respect to the metal. The transient scales grow by outward cation diffusion as evidenced by surface growth morphologies. The transformation to alpha-Al2O3 occurs within 1 hour at 1100C by a nucleation and radial growth process. The large volume decrease associated with the transformation results in a highly strained alpha-Al2O3 microstructure. A change in scale growth mechanism from outward cation to inward anion diffusion allows transient surface morphologies to be smoothed by surface diffusion. The mature stage of oxidation involves the growth of an alpha-Al2O3 scale having the lacey morphology formed as a result of the gamma yields alpha transformation. Growth of the scale occurs by counterdiffusion along grain boundaries resulting in ridges formed by impingement of alpha-Al2O3 nuclei during the transformation stage. Also scale growth occurs by inward oxygen diffusion through healed cracks; the cracks result from transformation stresses. The measured growth rates of scales having the lacey morphology are an order of magnitude less than fine-grained alpha-Al2O3 scales. Metal orientations were found to have a large effect on oxide morpholoies during all stages of oxidation.

Doychak, J. K.↗
NASA NTRS1988

Sampling the oxidative weathering products and the potentially acidic permafrost on Mars

Large areas of Mars' surface are covered by oxidative weathering products containing ferric and sulfate ions having analogies to terrestrial gossans derived from sulfide mineralization associated with iron-rich basalts. Chemical weathering of such massive and disseminated pyrrhotite-pentlandite assemblages and host basaltic rocks in the Martian environment could have produced metastable gossaniferous phases (limonite containing poorly crystalline hydrated ferric sulfates and oxyhydroxides, clay silicates and opal). Underlying groundwater, now permafrost on Mars, may still be acidic due to incomplete buffering reactions by wall-rock alteration of unfractured host rock. Such acidic solutions stabilize temperature-sensitive complex ions and sols which flocculate to colloidal precipitates at elevated temperatures. Sampling procedures of Martian regolith will need to be designed bearing in mind that the frozen permafrost may be corrosive and be stabilizing unique complex ions and sols of Fe, Al, Mg, Ni and other minor elements.

Burns, Roger G.↗
NASA NTRS1988

Containerless science for materials processing

Containerless materials processing in space to restrict specimen deformation from hydrostatic pressure of contact with the container is discussed. Several containerless science studies are reviewed, including the study of drop dynamics, nucleation studies, metastable solid phases experiments, glass research, biological materials research, and protein crystal growth. The development of technologies for materials research in space are examined, including acoustic containerless systems, and electrostatic and electromagnetic containerless processing.

Wang, T. G.↗
NASA NTRS1989

Transient oxidation of single-crystal beta-NiAl

The transient oxidation of beta-NiAl in air at 800 C and 1100 C has been studied using electron microscopy. The oxide scale consists predominantly of metastable Al2O3 phases. Theta-Al2O3 is the major oxide phase within 10.0 hr of oxidation at 800 C and 0.1 hr at 1100 C. The scales form epitaxially on (001) sub beta and (012) sub beta specimens throughout the transient stage, whereas the degree of preferred oxide orientation decreases with oxidation time on (011) sub beta and (111) sub beta specimens. The orientation relationships reflect the small mismatch between parallel close-packed directions in the metal and in the cation sublattice of the oxides. The correlation of distinctive oxide surface morphologies with internal structural defects indicates the strong tendency of the Al2O3 scale to grow via short-circuit diffusion paths.

Doychak, J.↗
NASA NTRS1989

Ordering in the Fe-Ni system under electron irradiation

The disorder-order transformation was generated in a range of Fe-Ni alloys using 1 MeV electrons in a high voltage electron microscope. The experimental factors that influence the occurrence of the transformation were determined, and the critical disordering temperature, Tc, was determined as a function of composition. It was demonstrated that the irradiation enhanced the ordering reaction kinetics. A metastable, ordered phase transformation was not induced. From the results, it is possible to deduce new information about the Fe-Ni phase diagram below 350 C.

Reuter, K. B.↗
NASA NTRS1994

Surfactant-based critical phenomena in microgravity

The objective of this research project is to characterize by experiment and theoretically both the kinetics of phase separation and the metastable structures produced during phase separation in a microgravity environment. The particular systems we are currently studying are mixtures of water, nonionic surfactants, and compressible supercritical fluids at temperatures and pressures where the coexisting liquid phases have equal densities (isopycnic phases). In this report, we describe experiments to locate equilibrium isopycnic phases and to determine the 'local' phase behavior and critical phenomena at nearby conditions of temperature, pressure, and composition. In addition, we report the results of preliminary small angle neutron scattering (SANS) experiments to characterize microstructures that exist in these mixtures at different fluid densities.

Kaler, Eric W.↗