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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 19 records

Melt Crystallization of CsF from Alkali Fluorides

Fractional melt-crystallization is a technique used to separate components in a multicomponent liquid mixture through controlled cooling. In fiscal year (FY) 2023, this technique was successfully used to separate CsCl from LiCl-KCl. This demonstrated a potential route for concentrating electrorefiner fission product waste streams in pyrochemical fuel cycles, building on previous work that developed the melt-crystallization system for fission product removal from LiCl-based electrolytes used for oxide reduction. This work investigated whether a thermally controlled process of a solid-liquid separation process could effectively remove CsF from LiF-NaF-KF (FLiNaK)-CsF salt for MSR fuel cycle applications. The designed process aimed to recover purified LiF-NaF-KF salt as solid precipitates while concentrating CsF to a remaining salt heel. This concentrated CsF can then be immobilized during a salt waste stream treatment operation, minimizing waste volume.

36 MATERIALS SCIENCE↗

Multistage nucleation pathway in LiF molten salt mirrors the crystal–melt interface structure

Despite over a century of studies, fundamental questions remain about the processes governing crystal nucleation from melts or solutions. Research over the past three decades has presented mounting evidence for kinetic pathways of crystal nucleation that are more complex than envisioned by the simplest forms of classical theory. Such observations have been presented for colloidal and elemental systems with covalent and metallic bonding. Despite the technological and geochemical importance of molten salts, similar studies for these ionically bonded systems are currently lacking. Here we develop a machine learning interatomic potential for a model ionic system: LiF. The potential features quantum-level accuracy for both liquid and multiple solid polymorphs over wide temperature and pressure ranges and accurately reproduces experimentally measured properties. Thanks to the efficiency of the potential, which enables microsecond-scale molecular dynamics simulations, induction times for nucleation of LiF solids from their melts are computed over a range of undercoolings. With the aid of a set of robust local order parameters established here, the simulations reveal that homogeneous crystal nucleation in undercooled melts preferentially initiates from liquid regions showing slow dynamics and high bond orientational order simultaneously, and the second-shell order of both precritical nuclei and the surface of postcritical nuclei is dominated by hexagonal close packing and body-centered cubic local structure, even though the nucleus core is dominated by face-centered cubic structure corresponding to the stable rocksalt crystal structure. Finally, we establish a connection between the crystallization pathway and the equilibrium crystal-melt interface structure.

Applied Physical Sciences↗

Correlative analysis of CsPbBr2Hal (Hal = Cl, Br, I) meltcrystallization paramete

Abstract — Metal halide perovskites (MHPs) are an exciting research topic as they have the potential to make solar cells that are both more efficient than current siliconbased designs and have a wider range of applications. In this work the crystallization of CsPbBr2Hal (Hal = Cl, Br, I) halide perovskite melts were studied by the differential thermal analysis method. It was established that the crystallization of CsPbBr2Hal (Hal = Cl, Br, I) melts can be “hot” (i.e., at temperatures above the point of the alloy’s start-melting temperature) or with supercooling. The replacement of the bromine atom with another halogen atom leads to a shift of the dwell temperature range, at which “hot” crystallization takes place, from 830-846 K for CsPbBr3 to 807-832 K for CsPbBr2Cl and 741-768 K for CsPbBr2I. The activation energy of “hot” crystallization decreases in the same order. A linear dependence between the pre-exponential factor (ln(𝑽𝑽𝒄𝒄𝒄𝒄𝒄𝒄𝒔𝒔𝒕𝒕 𝟎𝟎 )) and the activation energy (Ea) of the crystallization process is revealed from the experimental data, proving the compensation effect.

Kopach, O.↗

Melting and crystallization peculiarities in Cd0.50Mn0.50Te solid solutions

We investigated melting and crystallization processes of Cd0.50Mn0.50Te. Using differential thermal analysis (DTA) we studied the solid-liquid equilibrium temperature range, the temperature dependence of the volume fraction of the solid phase in the melt, and crystallization peculiarities. We observed that changing a dwell temperature from 1346 to 1354 K results in an increase of the crystallization temperature of the Cd0.50Mn0.50Te melt. Since the melt is in a semi-liquid state, its crystallization occurs over a solid-phase domain. It was found that a slightly overheated Cd0.50Mn0.50Te melt (up to 10 K) crystallizes more slowly than more overheated melts, and that the Cd0.50Mn0.50Te solid solutions are in a semi-liquid state in the temperature range of 1338 – 1354 K.

Kopach, Oleh↗

Progress towards a fully 3D, thermodynamically-consistent, constitutive model for volume changes during crystallization and melting of semicrystalline polymers

A thermodynamically-consistent constitutive model for semicrystalline polymers has been developed that is capable of representing volume strains from crystallization and melting. The new model is targeted at representing the thermal strain behavior of polymeric photo-voltaic module polymer encapsulation which may undergo crystallization and melting in their service environments. In the model, a homogenized material point is represented by a Gibbs free energy incorporating contributions from the crystalline phase, the amorphous phase, and mixing terms.

36 MATERIALS SCIENCE↗

Magnetism and quantum melting in moiré-material Wigner crystals

Recent experiments have established that semiconductor-based moir´e materials can host incompressible states at a series of fractional moir´e-miniband fillings. These states have been identified as generalized Wigner crystals in which electrons localize on a subset of the available triangular-lattice moir´e superlattice sites. In this article, we use momentum-space exact diagonalization to investigate the many-body ground state evolution at rational fillings from the weak-hopping classical lattice gas limit, in which only spin degrees-of-freedom are active at low energies, to the strong-hopping metallic regime where the Wigner crystals melt. We specifically address the nature of the magnetic ground states of the generalized Wigner crystals at fillings ν = 1/3 and ν = 2/3.

36 MATERIALS SCIENCE↗

Visualizing Uranium Crystallization from Melt: Experiment-Informed Phase Field Modeling and Machine Learning

The focus of this project was to observe and simulate the solidification of uranium metal at the crystallographic level from its molten state. Melting experiments were conducted at two different scales to observe microstructural evolution using either a laboratory-scale induction furnace (hundreds of grams of metal) or a microscope heating stage (hundreds of milligrams of metal), respectively. Experimental parameters and characterization data were then used to inform a phase field model of gamma-U crystal growth as dendrites with or without secondary phase impurities in the form of uranium carbide particles. Finally, training datasets were generated by the phase field model as inputs to a neural network, developed with the aim of providing a faster, cheaper surrogate model for microstructural simulations within a given parameter space. Progress is reported herein for each of these task areas. Ultimately, 1) an optical microscope heating stage capability has been stood-up for uranium metal solidification studies, 2) a phase field model was advanced to simulate multiple uranium grains growing in the presence of carbide impurity particles and 3) a neural network was constructed and optimized to predict the microstructure features of individually growing uranium crystals.

36 MATERIALS SCIENCE↗

Direct Observation of Two-Step, Stratified Crystallization and Morphology in Conjugated Polymer Thin Films

A two-step stratified crystallization process has been directly observed during cooling of poly(3-hexylthiophene) (P3HT) thin films of thickness h = 20-250 nm: a thin (<20 nm) layer at the free surface crystallizes ~25 °C higher than the bulk crystallization temperature (T C,bulk ), whereas the rest of the film (i.e. the underlayer) crystallizes near T C,bulk . In-situ measurements of films with and without a free surface unequivocally ascribe the high-temperature crystallization to a surface-induced process, which correlates with the formation of large birefringent structures and highly oriented edge-on crystallites at the air–polymer interface. In contrast, crystallization of the bulk-like underlayer leads to mostly edge-on-oriented crystallites in thinner films and becomes increasingly isotropic in thicker films. For h < 20 nm, free-surface effects dominate and only high-temperature crystallization is observed. These results highlight the potential of melt crystallization to tailor morphology and orientation across thin film thickness for specific electronic applications.

36 MATERIALS SCIENCE↗

Synthesis and Crystal Structures of Alkali (Na, Rb, Cs) Iron Phosphate Crystals

Three alkali-containing diphosphate crystals of A FeP 2 O 7 (A = Na, Rb, Cs) were synthesized through melt-crystallization. The crystal structures were determined using single-crystal X-ray diffraction (XRD) data. The synthesized diphosphates crystallized within the P 2 1 /c space group, and the structural parameters were compared to literature data of other A FeP 2 O 7 crystals within the P 2 1 /c space group.

36 MATERIALS SCIENCE↗

Product-specific kinetics reveal effect of epoxy crystallization on thermoset thermal degradation

Crystallization is a common problem for epoxy resins, which are ubiquitous in industrial and commercial use. Integration of crystallized epoxy monomers into cured thermosets has been shown to alter the thermosets’ final mechanical properties. However, no studies have investigated the impact of these crystals on the thermal stability of the thermoset. Here we investigate the degradation kinetics of a bisphenol F–based epoxy thermoset with and without crystallized monomers using Product-Specific Kinetic (PSK) analysis coupled with Evolved Gas Analysis-Mass Spectrometry (EGA-MS). PSK analysis revealed significant differences in evolved product ion kinetics, suggesting changes in the degradation kinetics between thermoset configurations. Further, it was concluded that early stages of degradation are influenced most by crystal presence due to the high concentration of unreacted epoxy monomers and lower cross-linking density of the cured network. After post-cure annealing, significant changes are observed in the degradation kinetics of thermosets without crystal inclusions. Conversely, post-cure annealing procedures of crystal integrated thermosets showed little change in the thermoset degradation kinetics across all conversion extents. These findings suggest that post-cure annealing of thermosets with crystals present at the onset does not alter the cross-linking density of the polymer network enough to significantly change the degradation kinetics. We hypothesize this is because the excess monomers from the melted crystals are unable to find suitable reaction sites for complete binding into the polymer network, which has direct implications for the material properties and final thermal stability of the thermoset.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mk-IV Salt Crystallization Hot Finger Apparatus for Partitioning Used Electrorefiner Salt

Electrorefining is a controlled redox process used to regulate the behavior of ionic species. Through this process, metals can be deposited onto a cathode from an electrolyte solution in a controlled manner. The Mk-IV electrorefiner (Mk-IV ER) at Idaho National Laboratory is an engineering-scale, molten salt-based electrorefining cell that has been used for decades to recover metallic uranium from spent fuel. As a result, highly stable fission product chlorides have accumulated in the electrolyte. This accumulation results in changes to the salt’s properties, such as melting temperature, thermal conductivity, and density, as well as elevated product impurity and fissile materials criticality margin. These factors prompt the need for a salt regeneration process, such as melt-crystallization and species drawdown. This work focuses on providing a conceptual design to regenerate ER salt from used Mk-IV-ER salt in-situ, while minimizing salt waste volumes by concentrating the fission products in a final processed salt heal. We propose using a hot-finger crystallization apparatus design to fractionally crystallize salt in the Mk-IV-ER head space (or baffle space), allowing the collection of solid and liquid fractions. By using a cup-drain design, the used salt will be allowed to slowly solidify on the walls of a stainless-steel cup. The apparatus drain plug will then open to allow the liquid salt phase to drain to a lower cup, effectively separating the liquid phase from the solid phase. Under the hypothesis that the liquid phase salt concentrates the fission products, which is under examination in the accompanying work package, this separation allows the recovered solid salt to be reused while minimizing the high-level salt waste volume of used ER salt.

36 - MATERIALS SCIENCE↗

Formation, cooling history and age of impact events on the IIE iron parent body: Evidence from the Miles meteorite

Most iron meteorites formed in planetary cores during differentiation, but the IIE iron meteorites have chemical and physical features that are inconsistent with this origin. By combining mineral chemistry, mineral modes and three-dimensional petrography, we reconstruct the bulk chemistry of the felsic silicate-bearing Miles IIE iron meteorite and demonstrate that the silicate inclusion compositions are similar to partial melts produced experimentally from an H chondrite composition. We use the reconstructed bulk composition, mineralogy and thermodynamic modelling to show that melting above ~ 1200°C under reducing conditions formed metal (Fe-Ni alloy) and felsic silicate partial melts. Upon cooling, the melts crystallized Mg-rich pyroxenes, Na- and K-rich feldspars, and tridymite. Importantly, this mechanism enriches cosmochemically volatile elements (i.e., those with a 50% condensation temperature of ~430–830°C, like Na and K) to the level found in the felsic silicate inclusions. The presence of crystallographically disordered srilankite (only stable above 1160°C) and an absence of Widmanstätten texture require both high peak temperatures and rapid cooling, which cannot be explained by core formation. Instead, they point to small melt volumes, a transient heat pulse, and small thermal mass, and imply efficient physical segregation of silicate and metallic melts through buoyancy separation followed by rapid cooling that arrested the separation of metal and silicate liquid phases. In situ 207 Pb/ 206 Pb age of 4542.3 ± 4.0 Ma in Zr-oxide and phosphate minerals dates the melting event that formed the silicate inclusions. This age aligns with the earliest ages found in other IIE iron meteorite silicates and requires a heating event ~25 million years after the solar system formed. We found 39 Ar/ 40 Ar ages of 3495 ± 52 Ma (low-T) and 4303 ± 7 Ma (high-T) in a K-feldspar grain, with the 3495 Ma age aligning with later thermal events recorded in other IIE iron meteorites. Dating reveals the complex petrogenetic and thermal history of Miles and the IIE iron meteorites. This is the first IIE iron meteorite found to record evidence of heating at 4.5 and 3.5 Ga likely from impact events. We propose that high-velocity impact(s) into an iron-rich, porous chondritic parent body at ~4.54 Ga produced immiscible metal and silicate melts that cooled rapidly and trapped low density silicate inclusions within high density metal. Other IIE irons that formed at lower peak temperatures (900–1000°C) contain chondritic silicate inclusions and relict chondrules, supporting this conceptual model. In conclusion, this petrogenesis is consistent with thermodynamic modelling, experimental data and the wide range of peak temperatures and cooling rates observed in the IIE iron meteorites.

58 GEOSCIENCES↗

Confocal Raman Microscopy for Measuring In Situ Temperature-Dependent Structural Changes in Poly(Ethylene Oxide) Thin Films

Crystallization from the melt is a critical process governing the properties of semi-crystalline polymeric materials. While structural analyses of melting and crystallization transitions in bulk polymers have been widely reported, in contrast, those in thin polymer films on solid supports have been underexplored. Herein, in situ Raman microscopy and self-modeling curve resolution (SMCR) analysis are applied to investigate the temperature-dependent structural changes in poly(ethylene oxide) (PEO) films during melting and crystallization phase transitions. By resolving complex overlapping sets of spectra, SMCR analysis reveals that the thermal transitions of 50 µm thick PEO films comprise two structural phases: an ordered crystalline phase and a disordered amorphous phase. The ordered structure of the crystalline PEO film entirely disappears as the polymer is heated; conversely, the disordered structure of the amorphous PEO film reverts to the ordered structure as the polymer is cooled. Broadening of the Raman bands was observed in PEO films above the melting temperature (67 °C), while sharpening of bands was observed below the crystallization temperature (45 °C). The temperatures at which these spectral changes occurred were in good agreement with differential scanning calorimetry (DSC) measurements, especially during the melting transition. The results illustrate that in situ Raman microscopy coupled with SMCR analysis is a powerful approach for unraveling complex structural changes in thin polymer films during melting and crystallization processes. Furthermore, we show that confocal Raman microscopy opens opportunities to apply the methodology to interrogate the structural features of PEO or other surface-supported polymer films as thin as 2 µm, a thickness regime beyond the reach of conventional thermal analysis techniques.

Koh, Miharu [Department of Chemistry, University o↗

Thermal behaviors of ethylene vinyl acetate encapsulants in fielded silicon photovoltaic modules

Aging of silicon photovoltaic (PV) module packaging is one of the greatest limiters of PV module service lifetimes. Module characterization typically focuses on power degradation metrics, which do not convey the complexities of often simultaneous degradation mechanisms. In this work, PV modules with pristine references and known fielding histories were investigated by non-destructive and destructive methods. Modules from Canadian Solar, Mission Solar, and Hanwha Q-Cells were fielded for up to three years; select modules were removed from fielding each year for coring to allow for characterization of the encapsulant. Modules are commonly encapsulated with two protective layers of partially-crystalline ethylene vinyl acetate (EVA) polymer that must undergo a crosslinking reaction to achieve desired properties. The extent of crystallinity of the encapsulants as studied by differential scanning calorimetry showed differences between manufacturers and over time. Some encapsulants showed different magnitudes of crystal sizes which changed after fielding; encapsulants with the monodisperse crystal sizes did not change with fielding. This is due to differences in thermal history. In conclusion, these results have implications for stress development during module aging, since EVA crystal melting and crosslinking reactions can result in encapsulant density changes.

36 MATERIALS SCIENCE↗

Light–Material Interactions Using Laser and Flash Sources for Energy Conversion and Storage Applications

Abstract This review provides a comprehensive overview of the progress in light–material interactions (LMIs), focusing on lasers and flash lights for energy conversion and storage applications. We discuss intricate LMI parameters such as light sources, interaction time, and fluence to elucidate their importance in material processing. In addition, this study covers various light-induced photothermal and photochemical processes ranging from melting, crystallization, and ablation to doping and synthesis, which are essential for developing energy materials and devices. Finally, we present extensive energy conversion and storage applications demonstrated by LMI technologies, including energy harvesters, sensors, capacitors, and batteries. Despite the several challenges associated with LMIs, such as complex mechanisms, and high-degrees of freedom, we believe that substantial contributions and potential for the commercialization of future energy systems can be achieved by advancing optical technologies through comprehensive academic research and multidisciplinary collaborations.

Materials Science↗

Stochastic symplectic reduced-order modeling for model-form uncertainty quantification in molecular dynamics simulations in various statistical ensembles

Here, this work focuses on the representation of model-form uncertainties in molecular dynamics simulations in various statistical ensembles. In prior contributions, the modeling of such uncertainties was formalized and applied to quantify the impact of, and the error generated by, pair-potential selection in the microcanonical ensemble (NVE). In this work, we extend this formulation and present a linear-subspace reduced-order model for the canonical (NVT) and isobaric (NPT) ensembles. The symplectic reduced-order basis is randomized on the tangent space of the Stiefel manifold to provide topological relationships and capture model-form uncertainty. Using the Large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS), we assess the relevance of these stochastic reduced-order atomistic models on canonical problems involving a Lennard-Jones fluid and an argon crystal melt.

42 ENGINEERING↗

Efficient machine learning interatomic potentials robust for liquid and multiple solid polymorphs of NaF and KF

Achieving atomic-level understanding of crystallization of molten salts is of importance to a wide range of technological applications. Recent work [Fan et al., Proc. Natl. Acad. Sci. USA 122, e2425702122 (2025)] revealed that crystal nucleation in molten LiF salt is a multistage process according to the molecular-dynamics (MD) simulations based on an atomic cluster expansion (ACE) machine-learning interatomic potential (MLIP). In order to understand the influence of increasing cation size on nucleation pathways and nucleation rates of molten fluoride salts, here we develop two new ACE MLIPs for NaF and KF. The two ACE MLIPs feature DFT-SCAN-level accuracy for liquid and multiple solid polymorphs over a wide temperature (0–2000 K) and pressure (0–100 GPa) range, and also reproduce well a number of experimental data for solid and liquid equilibrium properties. The efficiency of the two ACE MLIPs enable million-atom-scale or microsecond-scale MD simulations. The two general-purpose ACE MLIPs are expected to be useful for atomistic simulations for different purposes, in addition to studying crystallization of molten NaF and KF salts.

Crystal melting↗