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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 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

3D Printing ofThermally Responsive Shape Memory LiquidCrystalline Epoxy Networks

Abstract A two-component liquid crystalline epoxy network (LCEN) with shape memory behavior was developed and evaluated as a candidate material for 3D printing. The cure kinetics of the uncured material and the shape memory properties of the cured LCEN were investigated by using parallel plate rheology and dynamic mechanical analysis, respectively. A commercially available fumed silica additive was introduced to the neat, uncured material to improve the rheological properties for 3D printing. The addition of fumed silica was found to increase the yield stress, shear-thinning behavior, and toughness of the uncured epoxy ink. Polarized light microscopy, differential scanning calorimetry, and wide-angle X-ray scattering measurements between the neat and additive-modified LCEN suggested a reduction in liquid crystalline alignment in the modified LCEN, owing to interactions between crystalline domains and fumed silica, which in turn influenced the mechanical behavior. Overall, the additive was found to be successful in preserving the shape memory properties of LCEN while improving its printability.

Chemistry↗
DOE OSTI2026

The Synthesis and Ring-Opening Metathesis Polymerization of Energetic Norbornene Materials

Energetic norbornenes are promising candidates toward the development of new energetic polymers due to the synthetic versatility of norbornene ring-opening metathesis polymerizations used in commercial applications. We report the synthesis of two energetic norbornene materials that can be made in two steps with modest yields, containing either trinitroethanol or fluorodinitroethanol substituents. The norbornene monomers were then polymerized, and the polymers were characterized by Fourier transform infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC), contact angle measurements, and proton and carbon nuclear magnetic resonance spectroscopies ( 1 H and 13 C{ 1 H} NMR). Additionally, small-scale safety data consisting of electrostatic discharge (ESD), friction (FS), and impact (IS) sensitivities were measured for the norbornene monomers and their resulting polymers. These analyses revealed that energetic norbornene materials are relatively insensitive and have densities comparable to that of TNT (1.47–1.81 g·cm –3 ).

36 MATERIALS SCIENCE↗
DOE OSTI2025

Functional Design of Peptide Materials Based on Supramolecular Cohesion

Peptide materials offer a broad platform to design biomimetic soft matter, and filamentous networks that emulate those in extracellular matrices and the cytoskeleton are among the important targets. Given the vast sequence space, a combination of computational approaches and readily accessible experimental techniques is required to design peptide materials efficiently. Here, we report here on a strategy that utilizes this combination to predict supramolecular cohesion within filaments of peptide amphiphiles, a property recently linked to supramolecular dynamics and consequently bioactivity. Using established coarse-grained simulations on 10,000 randomly generated peptide sequences, we identified 3500 likely to self-assemble in water into nanoscale filaments. Atomistic simulations of small clusters were used to further analyze this subset of sequences and identify mathematical descriptors that are predictive of intermolecular cohesion, which was the main purpose of this work. We arbitrarily selected a small cohort of these sequences for chemical synthesis and verified their fiber morphology. With further characterization, we were able to link the latent heat associated with fiber to micelle transitions, an indicator of cohesion and potential supramolecular dynamicity within the filaments, to calculated hydrogen bond densities in the simulation clusters. Based on validation from in situ synchrotron X-ray scattering and differential scanning calorimetry, we conclude that the phase transitions can be easily observed by very simple polarized light microscopy experiments. We are encouraged by the methodology explored here as a relatively low-cost and fast way to design potential functions of peptide materials.

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

Dual Photoluminescence in Low-Temperature Phase of CsSnI 3 Nanocrystals

The expression of metal lone-pair electrons is hypothesized to underpin many of the interesting properties of inorganic halide perovskite semiconductors. Recently, a stable low-temperature monoclinic polar phase was predicted for CsSnBr 3 and CsSnI 3 , opening the possibility of direct investigation of a ferroelectric distorted structure compared to the undistorted structure. To date, there have been no experimental reports of such a structure in CsSnI 3 , and the low-temperature optical properties of CsSnI 3 nanocrystals have remained unexplored. Here we report optical and structural evidence of a phase transition around 240 K in 8.9 nm CsSnI 3 nanocrystals. Several changes in optical behavior occur below this transition point, including high-energy photoluminescence (PL) that emits concurrently with the exciton PL. The emergence of this high-energy PL is correlated with X-ray diffraction (XRD) and differential scanning calorimetry (DSC) supporting a phase transition from the orthorhombic structure between 240-200 K. Transient absorption measurements show an increase in the excited state lifetimes, i.e., slowed carrier cooling, at 200 K when photoexciting with photon energies above the high-energy state, consistent with slowed carrier cooling and emergence of high-energy PL. We hypothesize that the slowed carrier cooling is distinctive to this phase transition that modifies both the electronic and phonon structures that dictate excited-state carrier dynamics, and we discuss these changes.

14 SOLAR ENERGY↗
DOE OSTI2026

Lanthanide Separations through Helicate Self-Assembly

Skyrocketing demand for rare-earth elements makes their isolation and reuse from electronic waste an increasingly attractive alternative to mining. Typically, the capture of individual lanthanides from mixtures requires the iterative design of complex, macrocyclic ligands, a sometimes successful but often laborious process. Here we show that the self-assembly of rare-earth ions with a ditopic ligand, L d , results in the selective incorporation of smaller lanthanides and gives rise to impressive separation factors. Comparison to a monotopic ligand, L m , shows that the separation performance of ditopic L d critically depends on the presence of two adjacent binding sites. Isothermal titration calorimetry (ITC) experiments show that the selectivity of L d for smaller ions is thermodynamically driven and provide evidence of positive cooperativity among the two binding sites of L d . The simplicity of the separation procedure reported here, requiring only 1 min of sonication in methanol, shows the potential applicability of this approach to real-world separations. Here, by achieving efficient rare-earth separations in small, synthetically facile helicates, this work shows the promise of self-assembly as a mechanism to drive metal separations.

Alcohols↗
DOE OSTI2025

Navigating thermal stability intricacies of high-nickel cathodes for high-energy lithium batteries

High-nickel oxide cathodes, LiNi x M 1−x O 2 (x ≥ 0.8), are preferred in automotive lithium batteries, but they face thermal instability challenges. Inconsistent literature reports and unstandardized testing protocols further complicate quantitative assessments of the thermal stability of these cathodes. Here, we present here a statistical thermal analysis based on the differential scanning calorimetry measurements of 15 representative cathode materials with different compositions, morphologies and states of charge. The findings reveal that each cathode has a critical state of charge that defines its safe operating limit, which is affected by the metal–oxygen bond strength and surface reactivity. The thermal runaway temperature is dictated by the layered Li 1−x NiO 2 to LiNi 2 O 4 spinel-like phase transition, which is thermodynamically determined by the metal–oxygen bond covalency and kinetically influenced by the cation mixing and particle size. Raman spectroscopy is used to predict the thermal runaway temperature on the basis of the linear relationship between them. Finally, we propose a thermal stability index to quantify cathode thermal stability as a guide for developing safer high-nickel cathodes.

batteries↗
DOE OSTI2025

Theoretical and experimental quantification of Suzuki segregation enthalpy and strengthening mechanisms in a binary alloy

Solute segregation to planar defects in metallic alloys has been shown to drastically alter mechanical properties. While various works using first-principles and thermodynamic calculations have studied the fundamental driving forces for solute segregation via the Suzuki criterion, planar defect energy, or a comparison of energies of the HCP-like phase and FCC matrix, a quantitative experimental and computational comparison of equilibrium composition and segregation enthalpies has not yet been reported. In this work, we predict the equilibrium composition and segregation enthalpy to intrinsic stacking faults in a Ni-60Co (at.%) alloy and compare the results to two independent experimental methods. We observed that Co segregates to the innermost two planes of the intrinsic stacking fault, and we found that the experimental segregation enrichment, measured from transmission electron microscopy energy dispersive X-ray spectroscopy, of the faults is 6.8 at.% Co, which is 2.2 at.% less than the predicted value at the same temperature. We also find that the segregation enthalpy measured from the composition profile is −21.1 ± 6.4 meV/atom and separately from differential scanning calorimetry segregation enthalpy is −33.2 meV/atom, whereas the predicted enthalpy is −31 ± 1 meV/atom. Based on these results, we determine that segregation occurs very rapidly, within 8 min at temperatures as low as 36% of the homologous solidus temperature. Furthermore, this analysis provides an overview of the possible dislocation mechanisms responsible for strengthening effects due to solute segregation, and concludes that changes in room temperature hardness from local phase transformation is likely tied to post-segregation room temperature equilibrium partial separation distance.

Ab initio calculation↗
DOE OSTI2024

Non-covalent planarizing interactions yield highly ordered and thermotropic liquid crystalline conjugated polymers

Controlling the multi-level assembly and morphological properties of conjugated polymers through structural manipulation has contributed significantly to the advancement of organic electronics. In this work, a redox active conjugated polymer, TPT–TT, composed of alternating 1,4-(2-thienyl)-2,5-dialkoxyphenylene (TPT) and thienothiophene (TT) units is reported with non-covalent intramolecular S⋯O and S⋯H–C interactions that induce controlled main-chain planarity and solid-state order. As confirmed by density functional theory (DFT) calculations, these intramolecular interactions influence the main chain conformation, promoting backbone planarization, while still allowing dihedral rotations at higher kinetic energies (higher temperature), and give rise to temperature-dependent aggregation properties. Thermotropic liquid crystalline (LC) behavior is confirmed by cross-polarized optical microscopy (CPOM) and closely correlated with multiple thermal transitions observed by differential scanning calorimetry (DSC). This LC behavior allows us to develop and utilize a thermal annealing treatment that results in thin films with notable long-range order, as shown by grazing-incidence X-ray diffraction (GIXD). Specifically, we identified a first LC phase, ranging from 218 °C to 107 °C, as a nematic phase featuring preferential face-on π–π stacking and edge-on lamellar stacking exhibiting a large extent of disorder and broad orientation distribution. A second LC phase is observed from 107 °C to 48 °C, as a smectic A phase featuring sharp, highly ordered out-of-plane lamellar stacking features and sharp tilted backbone stacking peaks, while the structure of a third LC phase with a transition at 48 °C remains unclear, but resembles that of the solid state at ambient temperature. Furthermore, the significance of thermal annealing is evident in the ∼3-fold enhancement of the electrical conductivity of ferric tosylate-doped annealed films reaching 55 S cm −1 . More importantly, thermally annealed TPT–TT films exhibit both a narrow distribution of charge-carrier mobilities (1.4 ± 0.1) × 10 −2 cm 2 V −1 s −1 along with a remarkable device yield of 100% in an organic field-effect transistor (OFET) configuration. This molecular design approach to obtain highly ordered conjugated polymers in the solid state affords a deeper understanding of how intramolecular interactions and repeat-unit symmetry impact liquid crystallinity, solution aggregation, solution to solid-state transformation, solid-state morphology, and ultimately device applications.

Chemistry↗
DOE OSTI2025

Thermal management challenges in lithium-ion batteries: understanding heat generation mechanisms

This paper investigates heat generation in commercial 18 650 lithium-ion battery cells and the thermal management challenges from their high energy density and electrochemical processes. Thermal effects can degrade performance, accelerate aging, and increase thermal runaway risk. Using isothermal calorimetry and EIS, the study emphasizes optimizing thermal behavior to improve battery efficiency, safety, and durability.

25 ENERGY STORAGE↗
DOE OSTI2025

Stereogenic-at-silicon hybrid conjugated polymers

Stereoregularity in carbon-based polymers impacts critical physical properties such as crystallinity, but achieving comparable precision in polysilanes remains challenging. Herein, we report the synthesis of hybrid σ,π-conjugated polysilanes with defined stereoregularity, derived from cis- and trans-cyclosilane building blocks. Using Kumada polycondensation, we accessed a series of atactic, trans-enriched, and cis-enriched polysilanes, enabling a systematic investigation of how tacticity influences thermal and optical properties. Differential scanning calorimetry revealed distinct glass transition behaviors for stereoregular polymers compared to their atactic counterpart, and UV-vis spectroscopy demonstrated enhanced spectral resolution upon annealing of stereoregular films. A linear silane-based analog further underscored the structural impact of cyclic stereogenic units. These findings highlight how stereochemical precision in silicon-containing backbones can modulate macromolecular properties, opening avenues for the rational design of stereoregular polysilanes.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Deciphering supramolecular and polymer-like behavior in metallogels: real-time insights into temperature-modulated gelation and rapid self-assembly dynamics

Bis(pyridyl) urea-based gelators, namely L2 and its isomeric mixture ( L1 + L2 ), are known to self-assemble into 1D architectures capable of inducing supramolecular gelation. Coordination with metal ions such as Ag( I ), Cu( II ), and Fe( III ) introduces structural reinforcement, enabling the formation of distinct 3D networks governed by metal-specific coordination geometries. Here, we present a comprehensive investigation into the temperature-responsive behavior (20–60 °C) of L2 and L1 + L2 , both in the absence and presence of Ag( I ), Dy( III ), Fe( III ), Cu( II ), and Ho( III ), using real-time small-angle neutron scattering (SANS). To probe long-term structural evolution/kinetics of self-assembly, real-time small-angle X-ray scattering (SAXS) was employed on L2 + Ag gels, complemented by differential scanning calorimetry (DSC) to evaluate thermal transitions. Our results reveal strikingly divergent gelation behaviors: L2 forms a highly rigid, covalent polymer-like network, while L1 + L2 exhibits remarkable thermal adaptability. Upon metal coordination, the assemblies exhibit pronounced crystallinity and exceptional thermal stability, as evidenced by persistent Bragg reflections and invariant d-spacings. Intriguingly, L2 : Fe (2 : 1) and L1 : L2 : Fe (0.5 : 0.5 : 1) in acetonitrile-d 3 (ACN-d 3 ) deviate from this trend, forming thermally labile amorphous gels. These systems show a complete loss of crystalline order, reduced Porod exponents—indicative of collapsed or branched fiber morphologies—and prominent melting and glass transition events in DSC. Fitting SANS and SAXS data to the correlation length model unveiled insightful nanostructural features. While most systems displayed minimal temperature-induced variation in mesh size or surface morphology, L2 : Ag in dimethyl sulfoxide-d 6 (DMSO-d 6 )/D 2 O and L2 : Fe (1 : 1) in ACN-d 3 exhibited a rare combination of thermally stable correlation lengths and increasing high- q exponents—strongly suggesting progressive fiber densification or surface smoothing within a robust gel framework. These findings highlight the tunability and structural resilience of supramolecular gels through precise control of ligand architecture, metal coordination, and temperature, offering valuable design principles for functional soft materials.

Pajoubpong, Jinnipha [Univ. of Cincinnati, OH (Uni↗
DOE OSTI2026

Growth Strategy of a Hybrid Yb3Rh4Sn13/LaRuSn3 Structure Type: Integrating Thermal Analysis, In Situ Diffraction, and Geometric Descriptors

Remeika phases form a versatile family of cage like intermetallics built from transition metal–centered trigonal prisms linked into three dimensional frameworks that generate two characteristic voids: a large [AX₁₂] cuboctahedral cage hosting the rare earth ion and an [XX′₁₂] icosahedral cage accommodating the tetrel atom. In this work, we present a tool driven approach for targeted solid state synthesis of Remeika phases, integrating differential scanning calorimetry, in situ neutron diffraction, and a geometric tolerance factor that quantifies rare earth size compatibility within these polyhedral cages. When combined with arc melting and metallic flux crystal growth, this framework enables prediction, verification, and isolation of specific Remeika phases. Applying this strategy, we obtain single crystals of the predicted pseudo-perovskite Fe based Remeika compound Yb0.9FeGe3.1. More broadly, this perspective highlights how coupling real time structural probes with simple geometric descriptors provides a general pathway for designing synthesis conditions and accessing potentially metastable structure types in complex intermetallic systems.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Dry Deactivation of Sodium Metal in a Molten LiCl-KCl-CsCl-NaCl System

An experimental study was performed with the objective of investigating and characterizing a dry technique for deactivation of sodium metal in a molten salt system. The study was performed in three parts. First, proof-of-principle testing of the technique was performed at bench scale. It involved loading and melting tens of grams of clean sodium metal atop a pool of LiCl-KCl-CsCl eutectic at ∼300°C and then adding ammonium chloride particles while mixing. The ammonium chloride reacted with sodium to form sodium chloride and nitrogen/hydrogen off-gases. The sodium chloride assimilated into the salt pool, forming a quaternary salt mixture of LiCl-KCl-CsCl-NaCl. The proof-of-principle testing repeatedly exhibited complete deactivation of the loaded sodium metal. Second, characterization of a LiCl-KCl-CsCl-NaCl system was performed using differential scanning calorimetry to produce a partial phase diagram of LiCl-KCl-CsCl eutectic versus NaCl, which identified the liquidus, solidus, and two-phase regions of the quaternary system. Third, the dry deactivation technique was demonstrated at kg-scale in an inert atmosphere radiological glovebox with sodium metal that was previously separated in the same glovebox from uranium metal in unirradiated blanket elements for the Fermi-1 nuclear reactor. The quaternary salt product at the end of the demonstration was sampled and showed complete deactivation of the sodium metal. Here, in short, this study qualified a technique to completely deactivate batches of sodium metal in the absence of air or water. While this study focused on the deactivation of sodium metal, including bond sodium from unirradiated blanket elements, the technique is applicable to other sources of sodium metal, such as sodium metal from batteries. Furthermore, the technique could also be extended to other alkali metal systems, including lithium, sodium, potassium, rubidium, cesium, and mixtures thereof.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Phonon-mediated quantum efficiency measurement in semiconductors

Accurate quantum efficiency measurement not only provides crucial information for the photovoltaic cell industry but also supports experiments aimed at directly detecting dark matter and elastic neutrino interactions. The dark matter direct searches paradigm has recently expanded to include particles with masses below 1,MeV/c2, where the expected signal in an electron–recoil interaction is approximately in the eV range, just above the energy gap for silicon and germanium. A robust calibration method for ionization signals in this lower energy region is essential. This paper presents a method for measuring quantum efficiency and yield (q/E) in semiconductors using phonon-mediated calorimetry. The Neganov–Trofimov–Luke phonon amplification method in low-temperature semiconductor crystals has been employed to indirectly measure ionization down to single-electron accuracy. Specifically, at zero bias, the phonon readout directly quantifies the total energy deposited within the detector, independent of the ionization yield. This eliminates a significant source of systematic uncertainty in quantum efficiency estimates associated with total energy uncertainty. The paper includes results from an updated ionization efficiency measurement in a germanium detector.

Physics↗
DOE OSTI2024

Structure-driven development of a biomimetic rare earth artificial metalloprotein

The 2011 discovery of the first rare earth–dependent enzyme in methylotrophic Methylobacterium extorquens AM1 prompted intensive research toward understanding the unique chemistry at play in these systems. This enzyme, an alcohol dehydrogenase (ADH), features a La 3+ ion closely associated with redox-active coenzyme pyrroloquinoline quinone (PQQ) and is structurally homologous to the Ca 2+ -dependent ADH from the same organism. AM1 also produces a periplasmic PQQ-binding protein, PqqT, which we have now structurally characterized to 1.46-Å resolution by X-ray diffraction. This crystal structure reveals a Lys residue hydrogen-bonded to PQQ at the site analogously occupied by a Lewis acidic cation in ADH. Accordingly, we prepared K 142 A- and K 142 D-PqqT variants to assess the relevance of this site toward metal binding. Isothermal titration calorimetry experiments and titrations monitored by UV–Vis absorption and emission spectroscopies support that K 142 D-PqqT binds tightly (Kd = 0.6 ± 0.2 μM) to La 3+ in the presence of bound PQQ and produces spectral signatures consistent with those of ADH enzymes. These spectral signatures are not observed for WT- or K 142 A-variants or upon addition of Ca 2+ to PQQ ⸦ K 142 D-PqqT. Addition of benzyl alcohol to La 3+ -bound PQQ ⸦ K 142 D-PqqT (but not Ca 2+ -bound PQQ ⸦ K 142 D-PqqT, or La 3+ -bound PQQ ⸦ WT-PqqT) produces spectroscopic changes associated with PQQ reduction, and chemical trapping experiments reveal the production of benzaldehyde, supporting ADH activity. By creating a metal binding site that mimics native ADH enzymes, we present a rare earth-dependent artificial metalloenzyme primed for future mechanistic, biocatalytic, and biosensing applications.

Science & Technology - Other Topics↗
DOE OSTI2024

A molecular view of peptoid-induced acceleration of calcite growth

The extensive deposits of calcium carbonate (CaCO 3 ) generated by marine organisms constitute the largest and oldest carbon dioxide (CO 2 ) reservoir. These organisms utilize macromolecules like peptides and proteins to facilitate the nucleation and growth of carbonate minerals, serving as an effective method for CO 2 sequestration. However, the precise mechanisms behind this process remain elusive. In this study, we report the use of sequence-defined peptoids, a class of peptidomimetics, to achieve the accelerated calcite step growth kinetics with the molecular level mechanistic understanding. By designing peptoids with hydrophilic and hydrophobic blocks, we systematically investigated the acceleration in step growth rate of calcite crystals using in situ atomic force microscopy (AFM), varying peptoid sequences and concentrations, CaCO 3 supersaturations, and the ratio of Ca 2+ / HCO 3 − . Mechanistic studies using NMR, three-dimensional fast force mapping (3D FFM), and isothermal titration calorimetry (ITC) were conducted to reveal the interactions of peptoids with Ca 2+ and HCO 3 − ions in solution, as well as the effect of peptoids on solvation and energetics of calcite crystal surface. Our results indicate the multiple roles of peptoid in facilitating HCO 3 − deprotonation, Ca 2+ desolvation, and the disruption of interfacial hydration layers of the calcite surface, which collectively contribute to a peptoid-induced acceleration of calcite growth. These findings provide guidelines for future design of sequence-specific biomimetic polymers as crystallization promoters, offering potential applications in environmental remediation (such as CO 2 sequestration), biomedical engineering, and energy storage where fast crystallization is preferred.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗