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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Transient energy dissipation at the Fermi velocity in a magnetocaloric metal

Realizing fast energy dissipation in crystalline materials over macroscopic length scales is critical for energy-efficient devices and applications toward a carbon-neutral society but is usually dominated by electron-lattice interactions that cap the energy dissipation at the phonon velocity. Going beyond this velocity has been the focus of many studies, and the physical limit is the Fermi velocity where the energy is predominantly carried away by electrons throughout the materials. However, whether and how the Fermi velocity can be reached over macroscopic distances experimentally remain largely elusive. Here we show ultrafast energy dissipation at the Fermi velocity in the magnetocaloric metal LaFe 10.6 Co 1.0 Si 1.4 . Using time-resolved powder x-ray diffraction, we observe negative thermal expansion of the lattice throughout the micron-sized crystals in less than 600 fs with an incident optical fluence higher than 8 J cm -2 . The ultrafast timescale is in sharp contrast to the normal energy dissipation and shows the existence of a macroscopic momentum-relaxing electron mean free path immediately after the optical excitation. In conclusion, our findings open a different regime in energy dissipation and demonstrate the possibility of manipulating macroscopic material properties by strong optical pulses.

Chen, Yanna↗
DOE OSTI2025

Giant Negative Linear Compressibility in Orthorhombic Copper Cyanide

Most reported negative linear compressibility (NLC) materials exhibit either a small NLC over a large pressure range or a high NLC over a very small pressure range. Here, we report the remarkable discovery of giant NLC in the low-temperature form of CuCN (LT-CuCN) over an unusually large pressure range. High- pressure XRD studies on LT-CuCN observed the NLC of –20.5 TPa –1 along the a axis at zero pressure, and the ambient orthorhombic phase remained stable up to 9.8 GPa. Pressure- and temperature-dependent Raman studies identified the phonon vibrations responsible for NLC and negative thermal expansion (NTE).

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Symmetry Breaking and Ascending in the Magnetic Kagome Metal FeGe

Spontaneous symmetry breaking—the phenomenon in which an infinitesimal perturbation can cause the system to break the underlying symmetry—is a cornerstone concept in the understanding of interacting solid-state systems. In a typical series of temperature-driven phase transitions, higher-temperature phases are more symmetric due to the stabilizing effect of entropy that becomes dominant as the temperature is increased. However, the opposite is rare but possible when there are multiple degrees of freedom in the system. Here, we present such an example of a symmetry-ascending phenomenon upon cooling in a magnetic kagome metal FeGe by utilizing neutron Larmor diffraction and Raman spectroscopy. FeGe has a kagome lattice structure with simple A-type antiferromagnetic order below Néel temperature T N ≈ 400 K and a charge density wave (CDW) transition at T CDW ≈ 110 K , followed by a spin-canting transition at around 60 K. In the paramagnetic state at 460 K, we confirm that the crystal structure is indeed a hexagonal kagome lattice. On cooling to around T N , the crystal structure changes from hexagonal to monoclinic with in-plane lattice distortions on the order of 10 − 4 and the associated splitting of the double-degenerate phonon mode of the pristine kagome lattice. Upon further cooling to T CDW , the kagome lattice shows a small negative thermal expansion, and the crystal structure gradually becomes more symmetric upon further cooling. A tendency of increasing the crystalline symmetry upon cooling is unusual; it originates from an extremely weak structural instability that coexists and competes with the CDW and magnetic orders. These observations are against the expectations for a simple model with a single order parameter and hence can only be explained by a Landau free energy expansion that takes into account multiple lattice, charge, and spin degrees of freedom. Thus, the determination of the crystalline lattice symmetry as well as the unusual spin-lattice coupling is a first step towards understanding the rich electronic and magnetic properties of the system, and it sheds new light on intertwined orders where the lattice degree of freedom is no longer dominant. Published by the American Physical Society 2024

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

Evolution of structure and spectroscopic properties of a new 1,3-diacetylpyrene polymorph with temperature and pressure

A new polymorph of 1,3-diacetylpyrene has been obtained from its melt and thoroughly characterized using single-crystal X-ray diffraction, steady-state UV–Vis spectroscopy and periodic density functional theory calculations. Experimental studies covered the temperature range from 90 to 390 K and the pressure range from atmospheric to 4.08 GPa. Optimal sample placement in a diamond anvil cell according to our previously presented methodology ensured over 80% data coverage up to 0.8 Å for a monoclinic sample. Unrestrained Hirshfeld atom refinement of the high-pressure crystal structures was successful and anharmonic behavior of carbonyl oxygen atoms was observed. Unlike the previously characterized polymorph, the structure of 2°AP-β is based on infinite π-stacks of antiparallel 2°AP molecules. 2°AP-β displays piezochromism and piezofluorochromism which are directly related to the variation in interplanar distances within the π-stacking. The importance of weak intermolecular interactions is reflected in the substantial negative thermal expansion coefficient of -55.8 (57) MK -1 in the direction of C—H∙∙∙O interactions.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Autonomous Fracture Conductivity Using Expandable Proppants in Enhanced Geothermal Systems

Summary Early thermal breakthrough in enhanced geothermal systems (EGS) due to the presence of preferential flow channels is a major challenge that endangers efficient and economic heat extraction in such systems. Previous studies mainly focused on adjusting circulation rates of the working fluid, which still leaves significant amounts of untapped heat behind. Currently, there is a lack of technologies for altering flow distribution within the fracture network to achieve uniform heat sweeping in the reservoir. This work presents a novel concept for making proppants to autonomously control fracture conductivity based on the surrounding temperature. Here, proppants with negative thermal expansion coefficients have demonstrated the capability for appropriate fracture conductivity adjustment as a function of temperature to achieve uniform flow across the fracture network. Particle-particle interactions governing such functions are explicitly modeled, and then the Lattice Boltzmann methods (LBM) is used to determine the potential impact of closure stress and temperature changes on the permeability of the proposed proppant packs. Microscale analyses are further used to determine the required material properties to achieve a certain improvement in the permeability of the proppant pack. Our analyses show an enhancement in permeability and the associated fracture conductivity by half of their initial values. Field-scale analysis further confirms the effectiveness of the proposed concept as 31.4% more heat can be extracted from EGS over 50 years of production when the proposed proppants are used. Such novel proppants may effectively delay thermal breakthrough, sweep heat from larger rock volumes, and elongate the life span of the EGS project.

Engineering↗
DOE OSTI2021

Tuning Epoxy Thermomechanics via Thermal Isomerization: A Route to Negative Coefficient of Thermal Expansion Materials

Fine control over the thermal expansion and contraction behavior of polymer materials is challenging. Most polymers have large coefficients of thermal expansion (CTEs), which preclude long performance lifetimes of composite materials. Herein, we report the design and synthesis of epoxy thermosets with low CTE values below their T g and large contraction behavior above T g by incorporating thermally contractile dibenzocyclooctane (DBCO) motifs within the thermoset network. This atypical thermomechanical behavior was rationalized in terms of a twist-boat to chair conformational equilibrium of the DBCO linkages. We anticipate these findings to be generally useful in the preparation of materials with designed CTE values.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Chemical heterogeneity modulated zero thermal expansion alloy over super-wide temperature range

Chemical heterogeneity is usually avoided in solution chemistry, but it may still occur with sometimes dramatic effects on target materials and their properties. Here, we propose chemical heterogeneity as a counterintuitive strategy to design high-performance zero thermal expansion (ZTE) alloys. We apply this approach in a Hf-Ti-Fe alloy with excess Fe in the Hf/Ti sublattice and produce Hf/Ti concentration alternations at the micro level. Such chemical heterogeneity regulates local magnetic interactions in alloy and triggers a dispersed magnetic phase transition that modulates the thermal expansions at the micro level and hence results in a remarkable ZTE behavior over a super-wide temperature window from 10 to 480 K. This mechanism is supported by comprehensive studies on morphological microstructures, crystal and magnetic structures, and theoretical calculations. The strategy of local chemical heterogeneity opens up an avenue to design ZTE and the related functional materials directly via microstructure engineering.

36 MATERIALS SCIENCE↗
DOE OSTI2021

NUBOW-3D Demonstration on LFR: Final CRADA Report

The NUBOW-3D software was developed to assist in designing a core restraint system for sodium-cooled fast spectrum reactors. Originally conceived during the FFTF design activities, the United States has been a proponent of limited free bow reactor design ever since to improve safety performance. In fast spectrum reactors, successful safety performance during reactor transients requires favorable reactivity feedback that leads to safe power stabilization or even natural system shutdown. In fast spectrum reactors, one key mechanism that designers use to improve the performance is to make thermal expansion inject negative feedback into the reactor system. While most fast reactor systems generally have a negative reactivity response to geometric expansion, the NUBOW-3D software allows the designers to better explore the impact on reactivity and optimize the system to maximize its impact.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2023

An ab initio molecular dynamics study of varied compositions of the $\text{LiF-NaF-KF}$ molten salt

With increasing interest in molten salt reactors, there becomes a demand for investigations into thermophysical properties of salt systems. The LiF-NaF-KF (FLiNaK) salt system is a primary candidate for use in these reactors. However, the thermophysical properties of compositions outside the eutectic composition are still largely unknown. In this article, properties of ten unique compositions, including four ternary compositions, are investigated using ab initio molecular dynamics simulations across five temperatures between 900 K and 1300 K. The properties of interest are the density, thermal expansion, bulk modulus, compressibility, heat capacity, and enthalpy of mixing. In general, the results were found to be in good agreement with other literature and experimental results. The density and heat capacity had a tendency to be slightly underpredicted. No conclusions could be drawn about the bulk modulus and compressibility in terms of compositional dependence. The thermal expansion had a negative trend with respect to the LiF concentration and no trends were observed for the NaF or KF concentration. The enthalpy of mixing shows minima for the ternary compositions, with the near-equiatomic composition exhibiting the lowest values. Here this work shows the potential for compositional tailoring in the FLiNaK system to optimize thermophysical properties.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Lattice vibrations and energy landscape of the isoelectronic semiconductor series CuBr, ZnSe, GaAs, and Ge: The special case of CuBr and its $\mathcal{d}$-level chemistry

Here we have examined the lattice vibrations and the energy landscape of the isoelectronic diamond and zincblende semiconductor series CuBr, ZnSe, GaAs, and Ge. Vibrations are found to be an increasing function of ionicity, with the cation sublattice always vibrating more strongly than the anion sublattice. These findings are consistent with density functional theory (DFT) calculations of the energy landscape and temperature-dependent molecular dynamics simulations of the atomic-position fluctuations. For CuBr, inclusion of the Cu 3d Hubbard U term is found necessary to stabilize the zincblende structure and to bring its vibrational amplitudes into agreement with experiment. In addition, vibrations are found to strongly affect the CuBr near-edge x-ray absorption fine structure that we have successfully modeled by including displacements in our theoretical Bethe-Salpeter equation calculations. Reverse Monte Carlo structural refinements using large atomic configurations to simultaneously fit x-ray absorption and x-ray total-scattering data support these conclusions, and they reveal strong Cu-Br first-neighbor correlations and asymmetric distributions of interatomic distances in the temperature ranges of both negative and positive thermal expansion. Delineation of the CuBr valence band photoelectron spectrum into its Cu 3d and Br 4p states uniquely reveals their covalent mixing and further supports the DFT results.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Electronically driven collapse of the bulk modulus in δ -plutonium

Plutonium metal exhibits an anomalously large softening of its bulk modulus at elevated temperatures that is made all the more extraordinary by the finding that it occurs irrespective of whether the thermal expansion coefficient is positive, negative, or zero—representing an extreme departure from conventional Grüneisen scaling. We show here that the cause of this softening is the compressibility of plutonium’s thermally excited electronic configurations, which has thus far not been considered in thermodynamic models. We show that when compressible electronic configurations are thermally activated, they invariably give rise to a softening of the bulk modulus regardless of the sign of their contribution to the thermal expansion. The electronically driven softening of the bulk modulus is shown to be in good agreement with elastic moduli measurements performed on the gallium-stabilized δ phase of plutonium over a range of temperatures and compositions and is shown to grow rapidly at small concentrations of gallium and at high temperatures, where it becomes extremely sensitive to hydrostatic pressure.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Transformational challenge reactor design characteristics

The Transformational Challenge Reactor (TCR) program was conceived with the goal to reduce costs and time frames associated with advanced reactor deployment by leveraging developments in advanced manufacturing, advanced materials, data science, and rapid prototyping and testing. The final deliverable of the TCR program was to be an operational test of a novel reactor design. The TCR core design incorporates a dense tri-structural-isotropic/SiC fuel form and volumetrically efficient yttrium hydride moderator, both of which were manufactured and characterized under the TCR program. The TCR is a 3 MW{sub th} He-cooled experimental nuclear reactor designed to reach a total integrated burnup of less than 24 effective full-power hours to keep the radioactive source term to a very low level. TCR design process revealed a positive moderator coefficient; however, the negative doppler coefficients for the fuel and thermal expansion of fuel, moderator, and core support plate yield an overall negative reactivity coefficient. Calculated fuel element temperatures and stresses are well within safety margins. The maximum hypothetical accident (i.e., de-pressurized loss of forced cooling) yields only a modest increase in reactor temperatures that are all within safety margins. This paper summarizes the high-level TCR design characteristics, which were derived from neutronics, thermohydraulics, thermomechanics, and safety analyses.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2025

Thermodynamic origin of the pressure-induced Invar effect: General criterion and experimental study of Fe 68 ⁢Pd 32

Synchrotron X-ray diffraction measurements were performed on 57 Fe 68 Pd 32 at multiple pressures and two temperatures in a diamond-anvil cell. Between 4 and 11GPa, the thermal expansion was zero or slightly negative. This pressure-induced Invar effect was studied further with 57 Fe nuclear forward scattering and nuclear resonant inelastic X-ray scattering to obtain information on the pressure-induced changes in both the magnetization and the phonon density of states. Magnetic entropy and phonon entropy were obtained from these results, the latter with additional measurements from inelastic neutron scattering to account for the contributions from Pd atoms. The dependencies of these entropies on pressure gave the magnetic and phonon contributions to thermal expansion. These canceled in the region of pressure-induced Invar behavior, even though they individually increased by more than a factor of 2 below the Curie pressure. The behavior of phonons gives evidence for spin-phonon interactions in Fe 68 Pd 32 . A general explanation of the pressure-induced Invar effect is presented, showing that Invar behavior is typically expected at a pressure P* below a magnetic transition at pressure PC. The difference in pressure P C − P* scales with the fractional reduction in magnetic exchange interaction divided by the average Gr¨uneisen parameter.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2025

Atomistic Simulations of Thermal and Chemical Expansions of PrNi x Co 1‐x O 3‐δ Accelerated by Machine Learning Potentials

The electrodes and solid-state electrolytes in protonic ceramic electrochemical cells (PCECs) experience significant lattice expansions when exposed to high steam concentrations at elevated temperatures. In this paper, phonon calculations based on a new machine learning potential (MLP) are employed to elucidate the volume expansions of the proton-conducting PrNi x Co 1-x O 3-δ (PNC) lattices, manifested under a combined influence of oxygen vacancies (V$^{\cdot\cdot}_O$ ) and proton uptake (OH$^{\cdot}_O$ ) in the bulk at varying Ni/Co occupancies. It is revealed that the Ni/Co occupancy contributes to thermal and chemical expansions differently, where thermal expansions are related to Co occupancy. In contrast, chemical expansions are more closely associated with the Ni occupancy. Both V$^{\cdot\cdot}_O$ and OH$^{\cdot}_O$ lead to higher thermal expansions when compared to the pristine PNC. The temperature increase will negatively impact the hydration-induced chemical expansions. For combined thermal and chemical expansions, it is predicted that the strategies that boost the PCEC's electrochemical performance may harm the electrode–electrolyte interfacial stability, when the Ni occupancy is high, due to severe chemical expansions. Mitigating chemical expansions of the Ni-abundant PNC will benefit the interfacial stability. Finally, the presented computational methods for phonon calculations, based on emerging machine learning interatomic potential techniques are anticipated to have a lasting impact on future PCEC development.

computational prediction↗
DOE OSTI2025

Negative linear compressibility and complex phase behaviour in 7 Li 2 CO 3

We present a combination of neutron powder-diffraction measurements demonstrating negative linear compressibility and irregular thermal expansion in 7 Li 2 CO 3 . This is shown to be due to an interplay between the tilting of the rigid carbonate group and the shear strain in the unit cell, which leads to a first-order transition from monoclinic to hexagonal symmetry. The phase evolution is shown to be highly sensitive to the level of hydrostaticity in the sample. Under hydrostatic conditions, the sample begins transformation at 8.5 GPa leading to a change from tetrahedral to octahedral Li coordination. Symmetry adapted basis mode analysis, combined with density functional theoretical (DFT) calculations and Raman spectroscopy, is used to show that this transition is reverse proper ferroelastic in nature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗