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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Solid-state batteries enabled by ultra-high-frequency self-heating

Solid-state batteries (SSBs) are promising next-generation batteries due to their high energy density and enhanced thermal stability and safety. However, their sluggish kinetics and transport at room temperature result in high internal impedance and critically reduce the attainable discharge energy density. Taking advantage of their strong temperature-dependent ionic conductivity, here we introduce ultra-high-frequency (greater than 105 Hz) self-heating (UHFSH) of SSBs, which can rapidly warm up the batteries from room temperature to operating temperature (∼65°C) in less than a minute. As proof of concept, UHFSH experiments were conducted on symmetric solid-state cells with lithium aluminum germanium phosphate electrolyte in different configurations. Using an experimentally validated model, pack-level simulations predict fast heating (50 K/min) and minimized heating energy consumption (less than 4%). Without any modification of the materials or structure of the batteries, our non-intrusive self-heating strategy potentially enables SSBs to discharge more than 2-fold energy in 25°C ambient.

pulse heating↗
DOE OSTI2023

Quantized resistance revealed at the criticality of the quantum anomalous Hall phase transitions

In multilayered magnetic topological insulator structures, magnetization reversal processes can drive topological phase transitions between quantum anomalous Hall, axion insulator, and normal insulator states. Here we report an examination of the critical behavior of two such transitions: the quantum anomalous Hall to normal insulator (QAH-NI), and quantum anomalous Hall to axion insulator (QAH-AXI) transitions. By introducing a new analysis protocol wherein temperature dependent variations in the magnetic coercivity are accounted for, the critical behavior of the QAH-NI and QAH-AXI transitions are evaluated over a wide range of temperature and magnetic field. Despite the uniqueness of these different transitions, quantized longitudinal resistance and Hall conductance are observed at criticality in both cases. Furthermore, critical exponents were extracted for QAH-AXI transitions occurring at magnetization reversals of two different magnetic layers. The observation of consistent critical exponents and resistances in each case, independent of the magnetic layer details, demonstrates critical behaviors in quantum anomalous Hall transitions to be of electronic rather than magnetic origin. Our finding offers a new avenue for studies of phase transition and criticality in QAH insulators.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Transport anomalies in the layered compound BaPt 4 Se 6

We report a layered ternary selenide BaPt 4 Se 6 featuring sesqui-selenide Pt 2 Se 3 layers sandwiched by Ba atoms. The Pt 2 Se 3 layers in this compound can be derived from the Dirac-semimetal PtSe 2 phase with Se vacancies that form a honeycomb structure. This structure results in a Pt (VI) and Pt (II) mixed-valence compound with both PtSe 6 octahedra and PtSe 4 square net coordination configurations. Temperature-dependent electrical transport measurements suggest two distinct anomalies: a resistivity crossover, mimic to the metal-insulator (M-I) transition at ~150 K, and a resistivity plateau at temperatures below 10 K. The resistivity crossover is not associated with any structural, magnetic, or charge order modulated phase transitions. Magnetoresistivity, Hall, and heat capacity measurements concurrently suggest an existing hidden state below 5 K in this system. Angle-resolved photoemission spectroscopy measurements reveal a metallic state and no dramatic reconstruction of the electronic structure up to 200 K.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Thermal conductance of interfaces between titanium nitride and group IV semiconductors at high temperatures

Measuring the temperature dependence of material properties is a standard method for better understanding the microscopic origins for that property. Surprisingly, only a few experimental studies of thermal boundary conductance at high temperatures exist. This lack of high temperature data makes it difficult to evaluate competing theories for how inelastic processes contribute to thermal conductance. To address this, we report time domain thermoreflectance measurements of the thermal boundary conductance for TiN on diamond, silicon-carbide, silicon, and germanium between 120 and 1000 K. In all systems, the interface conductance increases monotonically without stagnating at higher temperatures. For TiN/SiC interfaces, G ranges from 330 to 1000 MW/m2-K, with a room temperature conductance of 750 MW/m2-K. The interface conductance for TiN/diamond ranges from 140 to 950 MW/m2-K. Notably, for all four interfacial systems, the conductance continues to increase with temperature even after all phonon modes in the vibrationally soft material are thermally excited. This observation suggests that inelastic processes are significant contributors to the thermal conductance in all four interfacial systems, regardless of whether the materials forming the interface are vibrationally similar or dissimilar. Our study fills a notable gap in the literature for how interfacial conductance evolves at high temperatures and tests burgeoning theories for the role of inelastic processes in interfacial thermal transport.

Physics↗
DOE OSTI2025

Structural transition and possible pressure-induced superconductivity in a suboxide La 5 Pb 3 O

Here, in this study, we report a structural phase transition and its interplay with superconductivity in the suboxide La 5⁢ Pb 3 ⁢O. Upon cooling through 𝑇 𝑡 = 225K, La 5⁢ Pb 3⁢ O transforms from a high-temperature 𝐼⁢4/mcm to a low-temperature 𝑃⁢4/ncc structure in which La-Pb dimerization along the 𝑐 axis occurs. This transition is accompanied by anomalies in the temperature dependence of electrical resistivity and specific heat. High-pressure electrical transport measurements reveal that hydrostatic pressure suppresses the structural transition and possibly induces superconductivity with a maximum superconducting temperature of 10 K. Density functional theory calculations show minimal changes in the electronic density of states and no gap opening at 𝐸 𝐹 across 𝑇 𝑡 , suggesting that the transition is driven by bonding effects rather than Fermi surface instability. These findings establish La 5⁢ Pb 3 ⁢O as a promising platform for exploring the interplay between weak structural transitions and superconductivity.

Yan, Jiaqiang [Oak Ridge National Laboratory (ORNL↗
DOE OSTI2023

Doping as a tuning mechanism for magnetothermoelectric effects to improve z T in polycrystalline NbP

Weyl semimetals combine topological and semimetallic effects, making them candidates for interesting and effective thermoelectric transport properties. Here, we present experimental results on polycrystalline NbP, demonstrating the simultaneous existence of a large Nernst effect and a large magneto-Seebeck effect, which is typically not observed in a single material at the same temperature. We compare transport results from two polycrystalline samples of NbP with previously published work, observing a shift in the temperature at which the maximum Nernst and magneto-Seebeck thermopowers occur, while still maintaining thermopowers of similar magnitude. Theoretical modeling shows how doping strongly alters both the Seebeck and Nernst magneto-thermopowers by shifting the temperature-dependent chemical potential, and the corresponding calculations provide a consistent interpretation of our results. Thus, we offer doping as a tuning mechanism for shifting magneto-thermoelectric effects to temperatures appropriate for device applications, improving zT at desirable operating temperatures. Furthermore, the simultaneous presence of both a large Nernst and magneto-Seebeck thermopower is uncommon and offers unique device advantages if the thermopowers are used additively. Finally, we also propose a unique thermoelectric device which would collectively harness the large Nernst and magneto-Seebeck thermopowers to greatly enhance the output and zT of conventional thermoelectric devices.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2020

High-Temperature Thermophysical Property Measurement of Proposed Gen3 CSP Containment Materials

Abstract The US Department of Energy (DOE) has sponsored an initiative to improve the thermal efficiency of Concentrating Solar Power (CSP) systems. To approach parity with conventional fossil fuel-based electricity generation, the operating temperature of the CSP power cycle must exceed 700°C with integrated thermal energy storage. The materials used to house this high-temperature heat transfer media must be thermally stable and corrosion resistant. However, the temperature-dependent thermophysical properties of commonly used containment materials (nickel alloys and alumina-based firebricks) are either not well known or poorly understood. In this report, the high-temperature thermal properties of thirteen (13) candidate containment materials proposed by the CSP community are tested using laser flash analysis and differential scanning calorimetry.

Brankovic, Sonja A.↗
DOE OSTI2023

CsPbBr3 perovskite single crystals for X- and -radiation detectors

Methods were developed for the synthesis and growth of halide lead perovskites CsPbBr3, which can be used as detectors of optical, X-ray, and -radiation. The growth of single crystals was carried out by the Bridgman method in quartz ampoules using zone-refined starting material. The electro-physical properties of the inorganic perovskite lead cesium tribromide CsPbBr3 were studied. Two types of structures with Cr/CsPbBr3/Ni rectifying and Ni/CsPbBr3/Ni ohmic contacts were fabricated. The resistivity of (  7×109 Ohmcm), and the activation energy of the dark conductivity (E  0.8 eV) were determined. From the measurements of the optical transmission spectra, the CsPbBr3 energy gap at 300 K was found to be Еg = 2.27 eV. The temperature dependence of the forbidden gap (Eg(T) = 2.4 - 4*10-4 T, eV) was also determined. A significant increase in photosensitivity for the Cr/CsPbBr3/Ni structure was observed at elevated temperatures. The Cr/CsPbBr3/Ni structures were shown to be sensitive to -radiation. The FWHM of the energy resolution for 241Am source was measured to be 15.8 keV.

Sklyarchuk, V.↗
DOE OSTI2024

High-Fidelity and High-Performance Computational Simulations for Rapid Design Optimization of Sulfur Thermal Energy Storage

Industrial process heating (IPH) accounts for approximately 70% of US manufacturing energy use and is primarily produced by fossil fuel combustion. Approximately 1500 TWht (approximately 60%) of IPH demand is in the temperature range of 100-300. Industrial applications in this temperature range include drying, hydrothermal processing, thermal enhanced oil recovery, food and beverage, bioethanol production, etc. Cost-effective thermal energy storage (TES) that increases the utilization of waste and renewable heat (solar, geothermal, etc.) could provide significant energy savings and reliable heat sources, decrease emissions, and increase US manufacturing competitiveness through reductions in fuel consumption. TES development has historically been dominated by technologies suitable for deployment with concentrating solar power (CSP). State-of-the-art thermal storage deployed commercially with power tower CSP plants uses a 60%/40% NaNO3/KNO3 molten salt and operates between temperatures of approximately 280 degrees Celsius and 570 degrees Celsius using a two-tank configuration. However, these nitrate salts are unsuitable for operation outside of this temperature range due to a high freezing point of approximately 220 degrees Celsius, and limits on high-temperature salt stability and corrosion resistance of containment alloys. Other materials being investigated for TES include those based on: (1) sensible energy storage (various molten salt compositions, inert solid particles, rocks or pebble beds, sulfur, water, concrete, graphite, etc.), (2) latent energy storage in materials that undergo solid-liquid phase change at relevant temperatures (organic materials for low-temperature applications, inorganic salts and/or metals for high-temperature applications), or (3) thermochemical energy storage (hydrides, hydroxides, carbonates, metal oxides, etc.). The application temperature and challenges pertaining to storage material and/or containment cost, energy density, long-term thermal and cyclic stability, and charge/discharge heat transfer effectiveness drive material selection for a given IPH or electricity generation application. Sulfur is a cheap commodity at $80/ton compared to $1100 - 1300/ton for conventional salts. When using a metric of storage cost per kWh, sulfur costs around 2-3 $/kWh. Previous sulfur TES development focused on high temperature (>600 degrees) concentrated solar power applications with sulfur encapsulated in pipes and flow of gaseous HTF (air) in the shell side. However, for lower-temperature IPH applications in the range of approximately 100-300 degrees Celsius Element 16 adopted a compact and scalable TES design with molten sulfur in the shell and HTF pipes submerged in the molten sulfur bath. The low-cost molten sulfur TES for dispatchable IPH has deployment potential for broad applications. The spatial and temporal evolution of the HTF and sulfur temperature is critical to the TES system performance, and thus detailed modeling can improve understanding of the performance and facilitate design improvements. Using high performance computing and computational fluid dynamics (CFD) a low-cost molten sulfur thermal energy storage (TES) system for industrial process heating (IPH) applications was developed. The unique challenges in CFD modeling of sulfur TES are the sharp property changes of sulfur relevant to the working temperatures. Above 159, liquid sulfur undergoes polymerization, and the viscosity of sulfur rapidly increases by several orders of magnitude between 159 degrees Celsius and 188 degrees Celsius, followed by a decrease in viscosity beyond 188 degrees Celsius due to thermal bound dissociation. In addition, various concentrations of H2S impurities can also modify sulfur viscosity. This numerical challenge is especially relevant to transient simulation of the sulfur TES charging and discharging processes as the extreme property variations limit the applicability of traditional heat transfer correlations. Transient CFD simulations including the temperature-dependent sulfur properties and geometric complexity of the TES design were used to predict the effect of natural convection during charging and discharging on the heat transfer process, sulfur temperature uniformity, charge/discharge rates, and performance of the storage devices. The CFD model was validated with experimental results for a full charge and discharge cycle. The work will show 3D and 2D simulation comparisons aimed to facilitate rapid design iterations and a machine learning based design optimization approach.

CFD↗
DOE OSTI2023

Universal and nonuniversal features of Bardeen-Cooper-Schrieffer theory with finite-range interactions

Here, we study analytic solutions to the Bardeen-Cooper-Schrieffer (BCS) gap equation for isotropic superconductors with finite-range interaction potentials over the full range of temperatures from absolute zero to the superconducting critical temperature 0 ≤ T ≤ T c . Using these solutions Δ (ε,T), we provide a proof of the universality of the temperature dependence of the BCS gap ratio at the Fermi level Δ (ε = 0,T)/T c . Moreover, by examining the behavior of this ratio as a function of energy ε, we find that nonuniversal features emerge away from the Fermi level, and these features take the form of a temperature-independent multiplicative factor F(ε), which is equal to Δ (ε,T)/Δ(ε = 0,T) up to exponentially small corrections, i.e., the error terms vanish like e -1/λ in the weak-coupling limit λ → 0. We discuss the model-dependent features of both F(ε) and T c , and we illustrate their behavior focusing on several concrete examples of physically relevant finite-range potentials. Comparing these cases for fixed coupling constants, we highlight the importance of the functional form of the interaction potential in determining the size of the critical temperature and provide guidelines for choosing potentials which lead to higher values of T c . We also propose experimental signatures which could be used to probe the energy dependence of the gap and potentially shed light on the underlying mechanisms giving rise to superconductivity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

The Sensitivity of PBX 9502 to Drilling Operations

Polymer-bonded explosive (PBX) 9502 (95% TATB, 5% Kel-F 800 by weight) is dry-drilled on a CNC milling machine and its thermomechanical response to varying feed rates, drilling speeds, and peck depths with 4 mm and 5 mm diameter drill bits is investigated. The tested samples are affixed to a force sensor that enables recording temporally resolved cutting forces and torques, and a drill-embedded thermocouple yields local temperature data. From the data, an empirical relationship between temperature changes and feed per revolution is developed, which reveals reduced temperatures in higher feed per revolution regimes for PBX 9502. The observed relationship allows extrapolating to temperatures for other hole diameters, indicating increased temperature for smaller diameter drilling across the board. Additional testing was performed with PBX 9501 (95% HMX, 2.5% Estane®, 2.5% BDNPA/BDNPF by weight), albeit over a reduced parameter space, which revealed the opposite behavior for the feed per revolution temperature dependence. It is concluded that both PBX 9502 and PBX 9501 can be dry-drilled efficiently beyond the limits of presently applicable US-DOE standards, where cutting interface temperatures remain far below material critical temperatures. Finally, data reveals that coolant usage in the drilling process for these materials provides a wide safety margin.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2021

Direct Measurement of the Selective Microwave-Induced Heating of Agglomerates of Dipolar Molecules: The Origin of and Parameters Controlling a Microwave Specific Superheating Effect

Agglomerates of polar molecules in nonpolar solvents are selectively heated by microwave radiation. The magnitude of the selective heating was directly measured by using the temperature dependence of the intensities of the Stokes and anti-Stokes bands in the Raman spectra of p-nitroanisole (pNA) and mesitylene. Under dynamic heating conditions, a large apparent temperature difference (ΔT) of over 100 °C was observed between the polar pNA solute and the nonpolar mesitylene solvent. This represents the first direct measurement of the selective microwave heating process. The magnitude of the selective microwave heating was affected by the properties of the agglomerated pNA. As the concentration of the pNA increases, the magnitude of the selective heating of the pNA was observed to decrease. This is explained by the tendency of the pNA dipoles to orient in an antiparallel fashion in the aggregates as measured by the Kirkwood g value, which decreased with increasing concentration. This effect reduces the net dipole moment of the agglomerates, which decreases the microwave absorption. After the radiation was terminated, the effective temperature of the dipolar molecules returned slowly to that of the medium. The slow heat transfer was modeled successfully by treating the solutions as a biphasic solvent/solute system. Based on modeling and the fact that the agglomerate can be heated above the boiling temperature of the solvent, an insulating layer of solvent vapor is suggested to form around the heated agglomerate, slowing convective heat transfer out of the agglomerate. Furthermore, this is an effect unique to microwave heating.

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

Octahedral Distortion and Excitonic Behavior of Cs 3 Bi 2 Br 9 Halide Perovskite at Low Temperature

The metal halide ionic octahedron, represented as [MX 6 ] $n$- (M = metal cation, X = halide anion), serves as the basic structural unit in halide perovskites and plays a crucial role in determining their optoelectronic and chemical properties. Thus, it is possible to correlate the responses of metal halide perovskites to various environmental stimuli with the dynamic behaviors of the [MX 6 ] $n$- octahedra. In this study, with the temperature-dependent single-crystal X ray diffraction (SCXRD) measurements on Cs 3 Bi 2 Br 9 2D halide perovskites, we can identify two classes of distortions through the lowering of temperature: intraoctahedral distortion, which is the off-centering of Bi 3+ cation within a [BiBr 6 ] 3– octahedron due to the Bi 3+ 6s 2 lone pair electrons, and interoctahedral distortion, which is the collective misalignments among the [BiBr 6 ] 3– building blocks. Free exciton (FE) and self-trapped exciton (STE) models are used to study the relationship between the distortion of octahedra in Cs 3 Bi 2 Br 9 and the corresponding changes in its optoelectronic properties, which transform from dominating blue emission above 100 K to red emission at 4 K. In conclusion, this work provides new insights into the excitonic behaviors of perovskites and suggests a possibility that we can design and rationalize the optical properties of halide perovskites by regulating the environmental stimuli based on the knowledge of behaviors of the individual [MX 6 ] $n$- building blocks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Twist-assisted all-antiferromagnetic tunnel junction in the atomic limit

Abstract Antiferromagnetic spintronics 1,2 shows great potential for high-density and ultrafast information devices. Magnetic tunnel junctions (MTJs), a key spintronic memory component that are typically formed from ferromagnetic materials, have seen rapid developments very recently using antiferromagnetic materials 3,4 . Here we demonstrate a twisting strategy for constructing all-antiferromagnetic tunnel junctions down to the atomic limit. By twisting two bilayers of CrSBr, a 2D antiferromagnet (AFM), a more than 700% nonvolatile tunnelling magnetoresistance (TMR) ratio is shown at zero field (ZF) with the entire twisted stack acting as the tunnel barrier. This is determined by twisting two CrSBr monolayers for which the TMR is shown to be derived from accumulative coherent tunnelling across the individual CrSBr monolayers. The dependence of the TMR on the twist angle is calculated from the electron-parallel momentum-dependent decay across the twisted monolayers. This is in excellent agreement with our experiments that consider twist angles that vary from 0° to 90°. Moreover, we also find that the temperature dependence of the TMR is, surprisingly, much weaker for the twisted as compared with the untwisted junctions, making the twisted junctions even more attractive for applications. Our work shows that it is possible to push nonvolatile magnetic information storage to the atomically thin limit.

Science & Technology - Other Topics↗
DOE OSTI2021

Enhancement and maximum in the isobaric specific-heat capacity measurements of deeply supercooled water using ultrafast calorimetry

Knowledge of the temperature dependence of the isobaric specific heat (C p ) upon deep supercooling can give insights regarding the anomalous properties of water. If a maximum in C p exists at a specific temperature, as in the isothermal compressibility, it would further validate the liquid–liquid critical point model that can explain the anomalous increase in thermodynamic response functions. The challenge is that the relevant temperature range falls in the region where ice crystallization becomes rapid, which has previously excluded experiments. Here, we have utilized a methodology of ultrafast calorimetry by determining the temperature jump from femtosecond X-ray pulses after heating with an infrared laser pulse and with a sufficiently long time delay between the pulses to allow measurements at constant pressure. Evaporative cooling of ~15-µm diameter droplets in vacuum enabled us to reach a temperature down to ~228 K with a small fraction of the droplets remaining unfrozen. We observed a sharp increase in C p , from 88 J/mol/K at 244 K to about 218 J/mol/K at 229 K where a maximum is seen. The C p maximum is at a similar temperature as the maxima of the isothermal compressibility and correlation length. From the C p measurement, we estimated the excess entropy and self-diffusion coefficient of water and these properties decrease rapidly below 235 K.

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

Annihilation-limited long-range exciton transport in high-mobility conjugated copolymer films

A combination of ultrafast, long-range, and low-loss excitation energy transfer from the photoreceptor location to a functionally active site is essential for cost-effective polymeric semiconductors. Delocalized electronic wavefunctions along π-conjugated polymer (CP) backbone can enable efficient intrachain transport, while interchain transport is generally thought slow and lossy due to weak chain–chain interactions. In contrast to the conventional strategy of mitigating structural disorder, amorphous layers of rigid CPs, exemplified by highly planar poly(indacenodithiophene-co-benzothiadiazole) (IDT-BT) donor-accepter copolymer, exhibit trap-free transistor performance and charge-carrier mobilities similar to amorphous silicon. Here, we report long-range exciton transport in HJ -aggregated IDTBT thin-film, in which the competing exciton transport and exciton–exciton annihilation (EEA) dynamics are spectroscopically separated using a phase-cycling-based scheme and shown to depart from the classical diffusion-limited and strong-coupling regime. In the thin film, we find an annihilation-limited mechanism with ≪100% per-encounter annihilation probability, facilitating the minimization of EEA-induced excitation losses. In contrast, excitons on isolated IDTBT chains diffuse over 350 nm with 0.56 cm 2 s −1 diffusivity, before eventually annihilating with unit probability on first contact. We complement the pump–probe studies with temperature-dependent photocurrent and EEA measurements from 295 K to 77 K and find a remarkable correspondence of annihilation rate and photocurrent activation energies in the 140 K to 295 K temperature range.

Shi, Yuping (ORCID:0000000318289415)↗
DOE OSTI2026

First-principles investigation of structure-property relationships in stable and metastable MXenes

Understanding the structure–property relationships in layered transition-metal carbides or nitrides, known as MXenes, is of critical importance for their rational design, synthesis, and application. However, the vast chemical and structural diversity of MXenes, stemming from their wide range of M and X elements, surface terminations, and different atomic coordination environments, makes it challenging to clearly understand these structure–property relationships. Here, in this work, we perform first-principles density functional theory (DFT) calculations and molecular dynamics (MD) simulations to comprehensively investigate the stability and a variety of physical properties of MXenes with different coordination environments. Using Ti- and Mo-based carbide MXenes as model systems, energetic calculations reveal that Ti-based MXenes are most stable in octahedral coordination, whereas Mo-based MXenes preferentially adopt prismatic coordination. This fundamental difference in preferred atomic coordination gives rise to markedly distinct properties between these two systems as a function of the fraction of octahedral and prismatic sites. For instance, the in-plane stiffness of Ti-based MXenes increases as octahedral coordination becomes dominant, but it decreases in the Mo-based MXenes under the same conditions. Additional stability analyses based on mechanical, lattice-dynamical, and temperature-dependent thermodynamic properties demonstrate that many metastable MXenes not only satisfy the strict stability criteria but can also undergo phase transitions among different structures and even become stabilized at elevated temperatures. Although surface terminations, such as F and O atoms, do not alter the energetic ordering or the overall stiffness trends among stable and metastable MXenes, they influence other material properties. For instance, O termination can induce semiconducting behavior in both stable and metastable Ti 2 ⁢CO 2 MXenes. This study significantly advances the fundamental understanding of structure–property relationships in MXenes and provides valuable guidance for developing coordination-based design principles to precisely engineer MXenes with improved properties.

Oyeniran, Noah [University of Alabama, Tuscaloosa,↗
DOE OSTI2022

Theory of thermal properties of magnetic materials with unknown entropy

Theoretical approaches to study thermal properties of magnetic materials typically require accurate models of magnetic interactions in order to define the entropy. Here we introduce a complementary approach for examining thermal properties in magnetic systems where an accepted model for such interactions does not exist. In place of a specific model for magnetic interactions, the approach integrates measurements of temperature dependent magnetization of the studied material into a first principles computational scheme. The approach calculates system pressure from thermally disordered microstates that properly incorporate vibrational and spin subsystems at each temperature as well as the coupling between these subsystems. We apply the approach to calculate phonon modes and to investigate the anomalously low thermal expansion of the classical Invar alloy, Fe 0.65 Ni 0.35 . Here, the calculated phonon dispersions for Invar are in excellent agreement with measured data. The Invar thermal expansion is shown to remain small between 50 K and room temperature, consistent with the experimentally observed low thermal expansion value in this same temperature range. This anomalously small thermal expansion is directly connected to a small positive contribution from lattice thermal disorder that is nearly canceled by a large negative magnetic disorder contribution. By contrast, calculations for bcc Fe show a much larger thermal expansion, consistent with experiment, which is dominated by a large contribution from lattice thermal disorder that is reduced only slightly by a small negative contribution from that of magnetism. These findings give insights into the unusual nature of magnetism and spin-lattice coupling in Invar and Fe. In addition, they give promising preliminary support to the presented new methodology as a complementary way to investigate thermal properties of magnetic materials. The success achieved on Invar and Fe motivates future testing of the approach on other magnetic materials.

36 MATERIALS SCIENCE↗