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Results for “metastable phase”

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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Effect of crystallite geometries on electrochemical performance of porous intercalation electrodes by multiscale operando investigation

Lithium-ion batteries are yet to realize their full promise because of challenges in the design and construction of electrode architectures that allow for their entire interior volumes to be reversibly accessible for ion storage. Electrodes constructed from the same material and with the same specifications, which differ only in terms of dimensions and geometries of the constituent particles, can show surprising differences in polarization, stress accumulation and capacity fade. Here, using operando synchrotron X-ray diffraction and energy dispersive X-ray diffraction (EDXRD), we probe the mechanistic origins of the remarkable particle geometry-dependent modification of lithiation-induced phase transformations in V2O5 as a model phase-transforming cathode. A pronounced modulation of phase coexistence regimes is observed as a function of particle geometry. Specifically, a metastable phase is stabilized for nanometre-sized spherical V2O5 particles, to circumvent the formation of large misfit strains. Spatially resolved EDXRD measurements demonstrate that particle geometries strongly modify the tortuosity of the porous cathode architecture. Greater ion-transport limitations in electrode architectures comprising micrometre-sized platelets result in considerable lithiation heterogeneities across the thickness of the electrode. These insights establish particle geometry-dependent modification of metastable phase regimes and electrode tortuosity as key design principles for realizing the promise of intercalation cathodes. Designing electrode architectures for Li-ion batteries that can be reversibly accessible for ion storage can be challenging. Using operando techniques the mechanistic origin of lithiation-induced phase transformations in a V2O5 model cathode is now clarified.

Luo, Yuting↗
DOE OSTI2024

The effects of high-pressure annealing on magnetostructural transitions and magnetoresponsive properties in stoichiometric MnCoGe

In this study, phase transitions (structural and magnetic) and associated magnetocaloric properties of stoichiometric MnCoGe have been investigated as a function of annealing pressure. Metastable phases were generated by annealing at 800 °C followed by rapid cooling under pressures up to 6.0 GPa. The x-ray diffraction results reveal that the crystal cell volume of the metastable phases continuously decreases with increasing thermal processing pressure, leading to a decrease in the structural transition temperature. The magnetic and structural transitions merge and form a first-order magnetostructural transition between the ferromagnetic orthorhombic and paramagnetic hexagonal phases over a broad temperature range (>80 K) spanning room temperature, yielding considerable magnetic entropy changes. These findings demonstrate the utility of thermal processing under high pressure, i.e., high-pressure annealing, to control the magnetostructural transitions and associated magnetocaloric properties of MnCoGe without altering its chemical composition.

Physics↗
DOE OSTI2023

Coherent light control of a metastable hidden state

Metastable phases present a promising route to expand the functionality of complex materials. Of particular interest are light-induced metastable phases that are inaccessible under equilibrium conditions, as they often host new, emergent properties switchable on ultrafast timescales. However, the processes governing the trajectories to such hidden phases remain largely unexplored. Here, using time- and angle-resolved photoemission spectroscopy, we investigate the ultrafast dynamics of the formation of a hidden quantum state in the layered dichalcogenide 1T-TaS 2 upon photoexcitation. Our results reveal the nonthermal character of the transition governed by a collective charge-density-wave excitation. Using a double-pulse excitation of the structural mode, we show vibrational coherent control of the phase-transition efficiency. Our demonstration of exceptional control, switching speed, and stability of the hidden state are key for device applications at the nexus of electronics and photonics.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Exploring structural transitions at grain boundaries in Nb using a generalized embedded atom interatomic potential

The advancement in experimental techniques, like the atom probe tomography and high resolution electron microscopy, is fueling interest in studying structural transformations of grain boundaries in metal and alloys to uncover correlations between mechanical properties and solute or impurity segregation to grain boundaries. Atomistic modeling is an important tool that can pinpoint the intricate dynamics of grain boundary phase transitions, but the lack of accurate interatomic potentials needed to simulate the complex dynamics of grain boundary structural transitions and identify different metastable phases has been the bottleneck. To this end, we use niobium as a model body centered cubic (BCC) metal and develop an interatomic potential to study grain boundary phase transitions. The potential for Nb is based on a generalization of the embedded atomic method potential and has sufficient flexibility to learn complex energy landscapes using a small set of training structures. We systematically test and validate the using data from ab initio density functional theory calculations and experiments. Using this potential, we calculate energies of multiple symmetric-tilt grain boundaries spanning a wide range of misorientation angles. Additionally, we explore different metastable structures of the Σ 27(552) [$1\overline{1}0$] grain boundary and use molecular dynamic simulations to study the coexistence of metastable phases and grain boundary transitions at finite temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Exotic silicon phases synthesized through ultrashort laser-induced microexplosion: Characterization with Raman microspectroscopy

Exotic metastable phases of silicon formed under high pressure are expected to have attractive semiconducting properties including narrow band gaps that open up novel technological applications. Confined microexplosions induced by powerful ultrashort laser pulses have been demonstrated as an advanced tool for the creation of new high-pressure phases that cannot be synthesized by other means. Tightly focused laser pulses are used to generate localized modifications inside the material structure, providing the possibility for precise controlled band-gap engineering. In this study, noninvasive Raman spectroscopy was used for analysis of laser-modified zones in silicon and to determine the metastable high-pressure phases contained. Low laser energies induced the formation of amorphous-only silicon, while higher energies led to crystalline silicon polymorphs within the modifications, albeit under considerable residual stress up to 4.5 GPa. The presence of the structurally similar r8-Si, bc8-Si, and bt8-Si phases is revealed, as well as other yet to be identified phases, and the stacking-related 9R Si polytype is evidenced, presumably stress-induced by the highly compressed laser-modified zone. The ab initio random structure searching approach is used to calculate the Raman signatures and to help identify different Si polymorphs. The findings of this study by Raman spectroscopy from ultrashort laser-induced microexplosion sites may yield insights into the local structure and properties of new silicon metastable phases and the prospect of utilizing exotic phases for extending current applications.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Formation of distinctive nanostructured metastable polymorphs mediated by kinetic transition pathways in germanium

High-pressure β -Sn germanium may transform into diverse metastable allotropes with distinctive nanostructures and unique physical properties via multiple pathways under decompression. However, the mechanism and transition kinetics remain poorly understood. Here, we investigate the formation of metastable phases and nanostructures in germanium via controllable transition pathways of β -Sn Ge under rapid decompression at different rates. High-resolution transmission electron microscopy reveals three distinct metastable phases with the distinctive nanostructures: an almost perfect st12 Ge crystal, nanosized bc8/r8 structures with amorphous boundaries, and amorphous Ge with nanosized clusters (0.8–2.5 nm). Fast in situ x-ray diffraction and x-ray absorption measurements indicate that these nanostructured products form in certain pressure regions via distinct kinetic pathways and are strongly correlated with nucleation rates and electronic transitions mediated by compression rate, temperature, and stress. This work provides deep insight into the controllable synthesis of metastable materials with unique crystal symmetries and nanostructures for potential applications.

36 MATERIALS SCIENCE↗
DOE OSTI2024

The self-annealing of irradiation induced defects in magnetite Fe 3 O 4 : Revealing reversible irradiation-induced disorder transformation through in situ TEM

This work reports heavy ion-irradiation effects in polycrystalline Fe 3 O 4 . For this matter, Fe/Fe 3 O 4 heterostructures were irradiated in situ in a transmission electron microscopy with 1 MeV Kr ions at 50 K. Evidence of cubic to monoclinic transformation (a.k.a Verwey transition) was recorded in some magnetite grains upon cooling the sample (around 90 K); however, most of the oxide grains retain their cubic spinel structure. Irradiation effects were analyzed in the cubic phase up to a maximum dose of 38 dpa without the sign of amorphization. The extinction of first-order reflections was recorded at doses below 1 dpa, indicating the formation of a new (metastable) phase with half of the lattice parameters compared to the unirradiated Fe 3 O 4 crystal. The formation of the new crystalline phase, which also presents a high resistance to amorphization, is related to the disordering of the cation lattice and the high mobility of the cation interstitials. The metastable phase readily recovers around 225 K during the natural warming of the sample from 50 K to room temperature.

Atom irradiation effects↗
NASA NTRS1982

Containerless processing of Nb-Ge alloys in a long drop tube

The thirty-two meter drop tube at the Marshall Space Flight Center was used to study the effect of zero gravity containerless processing on the structure and properties of materials. The concept involves the suppression of heterogeneous nucleation of solid in liquid and, therefore, solidification accompanied by large degrees of undercooling. Under these conditions metastable phases can be formed or, at the very least, unique nonequilibrium microstructures (containing equilibrium phases) with unique properties can be produced. The drop tube solidification was applied to niobium base alloys with emphasis on the Nb-Ge binary system in an effort to produce metastable phases with high superconducting transition temperatures in bulk specimens. In the past, only lower Ge alloys (Nb-13 a/o, Nb-18 a/o, and Nb-22 a/o) could be undercooled. Higher Ge alloys (e.g., Nb-25 a/o Ge and Nb-27 a/o Ge) can now be undercooled on a routine basis.

Bayuzick, R. J.↗
DOE OSTI2022

Snapshots of a light-induced metastable hidden phase driven by the collapse of charge order

Nonequilibrium hidden states provide a unique window into thermally inaccessible regimes of strong coupling between microscopic degrees of freedom in quantum materials. Understanding the origin of these states allows the exploration of far-from-equilibrium thermodynamics and the development of optoelectronic devices with on-demand photoresponses. However, mapping the ultrafast formation of a long-lived hidden phase remains a longstanding challenge since the initial state is not recovered rapidly. Here, using state-of-the-art single-shot spectroscopy techniques, we present a direct ultrafast visualization of the photoinduced phase transition to both transient and long-lived hidden states in an electronic crystal, 1T-TaS 2 , and demonstrate a commonality in their microscopic pathways, driven by the collapse of charge order. We present a theory of fluctuation-dominated process that helps explain the nature of the metastable state. Our results shed light on the origin of this elusive state and pave the way for the discovery of other exotic phases of matter.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Magnetocaloric Effect in Lightly‐Doped Fe 5 Si 3 Single Crystals

Abstract Development of promising new materials for above room temperature magnetic cooling applications relies on careful balancing of structure and composition to maximize accessible metastable phases that can drive a strong magnetocaloric effect (MCE). However, the working temperatures of these materials may fall outside of desired application windows. In this work, it is shown that it is possible to control metastable phase stability temperatures of Fe 5 Si 3 through selection of appropriate spin and charge doping. Here, the parent material's desired structure appears only within a narrow temperature range from 1098 to 1303 K. Doping with Mn and P is shown to allow stabilization of the parent's high temperature phase and resulting MCE to room temperature. The structural and magnetic properties, and the magnetocaloric effect of single crystal Fe 4.83 Mn 0.16 Si 2.91 P 0.09 (FMSP) are investigated experimentally and theoretically. A first‐order magneto‐elastic transition is observed at 348 K, where magnetic onset is accompanied by a change in lattice volume without an apparent change in crystal symmetry. Although the trace Mn and P doping are found to decrease the T C , the maximum magnetic entropy change Δ S Max ( T ) and the relative cooling power (RCP) of FMSP are enhanced compared to polycrystalline Fe 5 Si 3 . As a result, an intrinsically broader entropy change over a larger temperature span is generated in the lightly doped single crystal of Fe 5 Si 3 . The magnetic moment of the system is also enhanced. Density functional theory (DFT) calculations are performed to gain microscopic insights into the experimental findings. The results suggest that the hexagonal Fe 5 Si 3 is a new giant room temperature MCE material that is on par with La–Fe–Si and Fe‐Mn‐P‐Si systems.

36 MATERIALS SCIENCE↗
DOE OSTI2020

A Metastable CaSH 3 Phase Composed of HS Honeycomb Sheets that is Superconducting Under Pressure

Evolutionary searches have predicted a number of ternary Ca–S–H phases that could be synthesized at pressures of 100–300 GPa. P6 3 /mmc CaSH 2 , Pnma CaSH 2 , Cmc2 1 CaSH 6 , and I$\bar{4}$CaSH 20 were composed of a Ca–S lattice along with H 2 molecules coordinated in a “side-on” fashion to Ca. The H–H bond lengths in these semiconducting phases were elongated because of H 2 σ → Ca d donation, and Ca d → H 2 σ* back-donation, via a Kubas-like mechanism. P$\bar{6}$m2 CaSH 3 , consisting of two-dimensional HS and CaH 2 sheets, was metastable and metallic above 128 GPa. The presence of van Hove singularities increased its density of states at the Fermi level and concomitantly the superconducting critical temperature, which was estimated to be as high as ~100 K at 128 GPa. Furthermore, this work will inspire the search for superconductivity in materials based upon honeycomb HX (X = S, Se, Te) and MH 2 (M = Mg, Ca, Sr, Ba) layers under pressure.

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

Salt-Assisted 2H-to-1T' Phase Transformation of Transition Metal Dichalcogenides [plus supplemental information]

Phase engineering of nanomaterials (PEN) has demonstrated great potential in the fields of catalysis, electronics, energy storage and conversion, and condensed matter physics. Recently, transition metal dichalcogenides (TMDs) with unconventional metastable phases (e.g., 1T and 1T') have attracted increasing research interest due to their unique and appealing physicochemical properties. However, there is still a lack of a simple, universal, and controlled method for the preparation of large-scale and high-purity unconventional-phase TMD crystals, restricting their further fundamental study and practical applications. Here, a facile, one-step salt-assisted general strategy is reported for the controlled phase transformation of commercially available TMDs with conventional 2H phase, yielding a large amount of metastable 1T'-phase TMDs, including WS 2 , WSe 2 , MoS 2 , and MoSe 2 . It is found that the easily accessible metal salts, such as K 2 C 2 O 4 ·H 2 O, K 2 CO 3 , Na 2 CO 3 , Rb 2 CO 3 , Cs 2 CO 3 , KHCO 3 , NaHCO 3 , and NaC 2 O 4 , can be used to assist the 2H-to-1T' phase transformation, greatly simplifying the synthetic process for producing metastable 1T'-TMDs. Importantly, this method can also be used to prepare 1T'-TMD alloys, such as 1T'-WS 2x Se 2(1–x) . We report this newly developed strategy is robust and highly effective, which can also be used for the phase engineering of other materials with various polymorphs.

1T′ phase↗
DOE OSTI2021

Regeneration of Active Surface Alloys during Cyclic Oxidation and Reduction: Oxidation of H 2 on Pd/Ag(111)

The surface morphology and composition of a catalyst during excursions between oxidizing and reducing conditions can change substantially, especially in bimetallic alloys. Both thermodynamic and kinetic factors play a role in determining the properties of alloy surfaces where the active phase may be a metastable state. Previously, Ag oxide reduction was shown to be dramatically enhanced when Pd is on the surface; however, Pd is more stable when dissolved in Ag, raising the question as to whether a highly active Pd surface state will persist over multiple reaction cycles—a requirement for catalytic function. Experiments herein demonstrate that the enhanced chemical functionality due to the presence of Pd on the surface is retained, based on the enhanced rate of silver oxide reduction over multiple oxidation/reduction cycles for a Pd/Ag(111) model. Repeated oxidation and reduction promote PdAg alloying and reversible structural and compositional changes are detected using X-ray photoelectron spectroscopy. Furthermore, this study establishes that metastable phases can persist in reactive processes on surfaces, indicating their potential in heterogeneous catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

A metastable tetragonal phase in two-dimensional halide perovskite lattices driven by a coherent Higgs mode

The optoelectronic properties of metal halide perovskites are defined by their coupled structural and photophysical properties, yet their lattice behaviour remains underexplored. Here, using impulsive stimulated Raman spectroscopy, we study light-induced phonon dynamics of two-dimensional butylammonium lead iodide ((BA) 2 PbI 4 ) films under varying excitation intensities, photon energies and temperatures. We reveal that, whereas (BA) 2 PbI 4 exhibits two thermally accessible orthorhombic phases, optically excited phonons transiently direct the lattice to a distinct, higher symmetry tetragonal phase. We show that bandgap oscillations arise from simultaneous distortions of in-plane and out-of-plane octahedral tilt angles with oscillations following a low-to-high symmetry pathway, marked by two vibrational frequencies independent of intensity—a signature of an optically excited Higgs mode. Notably, the Higgs mode at below-bandgap excitation induces a fourfold larger spectral shift than above-bandgap, where photogenerated charge carriers drive the system away from the optically induced tetragonal phase. This study illustrates how optomechanical coupling influences the optical properties of two-dimensional perovskites.

36 MATERIALS SCIENCE↗
DOE OSTI2022

A review of the metastable omega phase in beta titanium alloys: the phase transformation mechanisms and its effect on mechanical properties

Since its discovery in 1954, the omega (ω) phase in titanium and its alloys has attracted substantial attention from researchers. The β-to-ω and ω-to-α phase transformations are central to β-titanium alloy design, but the transformation mechanisms have been a subject of debate. With new generations of aberration-corrected transmission electron microscopy and atom probe tomography, both the spatial resolution and compositional sensitivity of phase transformation analysis have been rapidly improving. Furthermore, this review provides a detailed assessment of the new understanding gained and related debates in this field enabled by advanced characterization methods. Specifically, new insights into the possibility of a coupled diffusional-displacive component in the β-to-ω transformation and key nucleation driving forces for the ω-assisted α phase formation are discussed. Additionally, the influence of ω phase on the mechanical properties of β-titanium alloys is also reviewed. Lastly, a perspective on open questions and future direction for research is discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Influence of nanoscale interfaces on the dynamic deformation and spall failure of Cu–Fe alloy microstructures

Additively manufactured immiscible Cu–Fe alloys can exhibit a distribution of nanoscale interfaces due to the distribution of nanoscale clusters in the equilibrium and metastable phases. Molecular dynamics simulations investigate the role of such interfaces on the phase stability and transformation behavior during shock compression, as well as the mechanisms of damage nucleation during spall failure. The model multiphase Cu–Fe systems studied here comprise a distribution of Fe clusters in an FCC Cu matrix, as well as Cu clusters in a BCC Fe matrix. The length scales of the nanoscale clusters determine the energetics of the interfaces that can result in FCC/BCC (equilibrium) or FCC/FCC (metastable) interfaces in the Cu system matrix, and BCC/FCC (equilibrium) or BCC/BCC (metastable) interfaces in the Fe matrix. The MD simulations demonstrate that nanoscale metastable interface microstructures can induce plastic deformation and also stabilize phases or suppress phase transformations in metastable phase clusters. In contrast, equilibrium interfaces can influence phase transformation thresholds and serve as additional void nucleation sites during failure.

36 MATERIALS SCIENCE↗