The high thermal stability of a thermoelectric material, which maintains a stable conversion efficiency under prolonged heat exposure, is essential for sustainable thermoelectric applications. Despite the well-known relationship between thermal degradation and microstructural evolution, their underlying interplay remains unclear, with contradictory findings reported in the literature owing to the complex dependence of microstructural changes on the material composition. Herein, the effect of Sb doping on the thermal stability of NbCoSn half-Heusler compounds is investigated in detail by comprehensively analyzing their microstructural evolution. The results reveal that introducing 3.3 at.% Sb into NbCoSn markedly enhances the thermal stability, by preserving the lattice thermal conductivity after heat exposure. Advanced techniques, including atom probe tomography, scanning transmission electron microscopy, and neutron diffraction, show that this improvement is driven by the evolution of Sb-induced complementary point defects. Although heat exposure significantly reduces lattice disorder in intrinsic NbCoSn, NbCoSn_0.9Sb_0.1 retains its lattice disorder by forming alternative point defects, thereby maintaining its lattice thermal conductivity. This detailed experimental work, corroborated by ab initio calculations, highlights the pivotal role of the point defect dynamics in achieving robust thermoelectric performances in half-Heusler compounds for high-temperature applications.

The issue of hydrogen embrittlement (HE) in face-centered (FCC) structured alloys is significant for H storage and transportation application due to unanticipated damage beyond its predicted service life. This unpredictable situation may harm human life and limit hydrogen to a reliable source of renewable energy in industrial fields. Recent research has suggested that multi-principal element alloys possess high resistance to HE. However, there has been limited exploration of how their unique properties affect the HE mechanisms. In this study, using simple model VCrCoNi alloys with analogous grain sizes, the reduction rate of ductility by hydrogen uptake was measured through a slow strain rate tensile test following electro-chemical H charging. Further, the origin of HE resistance was investigated by analyzing various factors such as hydrogen contents, fracture and deformation behaviors, and grain boundary properties using thermal desorption spectroscopy, scanning electron microscope, and electron backscatter diffraction. Despite the consistent trends of the H content, stacking fault energy, and stress with increasing V content, the resistance to HE is the highest for the alloy with an intermediate ratio of V and Cr, namely, for the V_0.7Cr_0.3CoNi alloy. Through the analysis of grain boundary characteristics, the high resistance is attributed to large fractions of special boundaries and special triple junctions and large twin-related domain size, which suppresses crack growth and interlinkage. The favorable grain boundary characteristics result from mechanical dynamic recovery, achieved by the competitive effects of solid-solution strengthening and stacking fault energy. Thus, the present study provides novel insights into enhancing HE resistance in FCC-structured alloys.

Layered nanocomposite material having fcc-bcc interface with Kurdjumov-Sachs interface orientation relation has shown great potential as radiation resistant structural material for future fusion energy reactors. The superior radiation resistant properties of this material are attributed to it’s special fcc-bcc interface structure. In this study we have reported a stable interface between conventional bcc phase of Nb and transformed bcc phase of Cu. This bcc-bcc interface is found to be stable from both strain-energy and dynamical stability analysis. We have also shown that the bcc-bcc interface has different defect energetics behaviour compared to previously reported fcc-bcc interface which has a negative impact on the self annihilation property of the material against radiation induced defects. These aspects should be carefully considered in the future design of robust layered material for extreme radiation environment.

The thermodynamic stability of the premartensite (PM) phase has been a topic of extensive investigation in shape memory alloys as it affects the main martensite phase transition and the related physical properties. In general, the PM phase is stable over a rather narrow temperature-composition range. We present here evidence for chemical pressure induced suppression of the main martensite transition and stabilization of the PM phase over a very wide temperature range from 300 to ∼5K in a magnetic shape memory alloy (MSMA), Ni50Mn34In16, using magnetic susceptibility, synchrotron x-ray powder diffraction (SXRPD) studies, and first-principles calculations. The ac-susceptibility studies show a highly skewed and smeared peak around 300 K without any further transition up to the lowest temperature of our measurement (5 K) for ∼5% Al substitution. The temperature evolution of the SXRPD patterns confirms the appearance of the PM phase related satellite peaks at T≤300K without any splitting of the main austenite (220) peak showing preserved cubic symmetry. This is in marked contrast to the temperature evolution of the SXRPD patterns of the martensite phase of the Al free as well as ∼3% Al substituted compositions where the austenite (220) peak shows a clear splitting due to Bain distortion signalling symmetry breaking transition. Our theoretical calculations support the experimental findings and reveal that the substitution at the In site by a smaller size atom, like Al, can stabilize the PM phase with preserved cubic symmetry. Our results demonstrate that Al-substituted Ni-Mn-In MSMAs provide an ideal platform for investigating the physics of various phenomena related to the PM state.

Half-Heusler semiconductors satisfying 18-electron rule typically display promising characteristics for thermoelectric applications. A persistent inconsistency between the type of charge carriers in some of these alloys as obtained from experiment and theory however casts serious doubt on the computational prediction of new and efficient half-Heusler alloys. To gain insights into the origin of this disparity, we have investigated the effect of intrinsic point defects on the electronic structure of four frequently studied half-Heusler alloys of the form XYZ with Y being Ni or Co. Using state-of-the-art ab initio calculations, our study reveals that interstitial Ni and Co are energetically most stable point defects in these alloys. Remarkably, interstitial defect modifies the location of the Fermi level inside the band gap as well as the value of the band gap, thereby bringing in close agreement with the corresponding experimental result. This work thus highlights the decisive role played by interstitial defects in thermoelectric half-Heusler alloys, which may open a new avenue for deliberately utilizing these defects as a strategy for tailoring electronic structure and hence the corresponding thermoelectric properties.

Since its first emergence in 2004, the high-entropy alloy (HEA) concept has aimed at stabilizing single- or dual-phase multi-element solid solutions through high mixing entropy. Here, this strategy is changed and renders such massive solid solutions metastable, to trigger spinodal decomposition for improving the alloys’ magnetic properties. The motivation for starting from a HEA for this approach is to provide the chemical degrees of freedom required to tailor spinodal behavior using multiple components. The key idea is to form Fe-Co enriched regions which have an expanded volume (relative to unconstrained Fe-Co), due to coherency constraints imposed by the surrounding HEA matrix. As demonstrated by theory and experiments, this leads to improved magnetic properties of the decomposed alloy relative to the original solid solution matrix. In a prototype magnetic FeCoNiMnCu HEA, it is shown that the modulated structures, achieved by spinodal decomposition, lead to an increase of the Curie temperature by 48% and a simultaneous increase of magnetization by 70% at ambient temperature as compared to the homogenized single-phase reference alloy. The findings thus open a pathway for the development of advanced functional HEAs.

Tailoring nanostructures is nowadays a common approach for enhancing the performance of thermoelectric Heusler compounds by decreasing the thermal conductivity without significantly affecting the electrical conductivity. However, the most widely reported method for obtaining nanostructured thermoelectrics, an approach based on crushing as-cast alloy ingots followed by sintering of the debris, only gives limited control of the final nanostructure due to residual elemental segregation after casting. Here, a novel approach for fabricating nanostructured Heusler compounds is presented, which is based on crystallizing an amorphous precursor of NbCo_1.1Sn composition. This method yields two distinct nanostructures, namely one comprising only half-Heusler grains and another one comprising half-Heusler grains and full-Heusler nano-precipitates. The latter sample exhibits enhanced negative Seebeck coefficients as compared to the former over a wide temperature range. Using advanced characterization techniques, such as high-resolution transmission electron microscopy and atom probe tomography, in conjunction with ab initio density functional theory, detailed insights into the nanostructure and electrical properties of the specimens are provided. Filtering of low energy and mobility electrons at the half-Heusler and full-Heusler interface along with the formation of Co interstitial defects in the half-Heusler matrix are proposed to be the possible causes for the enhanced Seebeck coefficient of the nano-precipitate containing specimen.

Negative stacking fault energies (SFEs) are found in face-centered cubic high-entropy alloys with excellent mechanical properties, especially at low temperatures. Their roles remain elusive due to the lack of in situ observation of nanoscale deformation. Here, the polymorphism of Shockley partials is fully explored, assisted by a new method. We show negative SFEs result in novel partial pairs as if they were in hexagonal close-packed alloys. The associated yield stresses are much higher than those for other mechanisms at low temperatures. This generalizes the physical picture for all negative-SFE alloys.

We reveal the impact of magnetic ordering on stacking fault energy (SFE) and its influence on the deformation mechanisms and mechanical properties in a class of nonequiatomic quinary Mn-containing compositional complex alloys or high entropy alloys (HEAs). By combining ab initio simulation and experimental validation, we demonstrate magnetic ordering as an important factor in the activation and transition of deformation modes from planar dislocation slip to TWIP (twinning-induced plasticity) and/or TRIP (transformation-induced plasticity). A wide compositional space of Cr20MnxFeyCo20Niz(x+y+z=60, at. %) was probed by density-functional theory calculations to search for potential alloys displaying the TWIP/TRIP effects. Three selected promising HEA compositions with varying Mn concentrations were metallurgically synthesized, processed, and probed for microstructure, deformation mechanism, and mechanical property evaluation. The differences in the deformation modes of the probed HEAs are interpreted in terms of the computed SFEs and their dependence on the predicted magnetic state, as revealed by ab initio calculations and validated by explicit magnetic measurements. It is found that the Mn content plays a key role in the stabilization of antiferromagnetic configurations which strongly impact the SFEs and eventually lead to the prevalent deformation behavior.

The lattice dynamics in magnetic materials, such as Fe depends on the degree of disorder of the atomic magnetic moments and the time scale of spin fluctuations. Using first-principles methods, we have studied this effect by determining the force constant matrix in two limits: (i) When spin fluctuations are much faster than the atom vibrations, their combined impact is captured by a spin-space averaged force constant matrix, (ii) when individual spin fluctuations are sufficiently slow to scatter the phonon modes, the itinerant coherent potential approximation with spin-pair resolved force constants (i.e., φ↑↑,φ↓↓, and φ↑↓) is employed in this paper. The physical consequences for the vibrational spectral functions are analyzed by systematically modifying the input parameters (magnetization and ratio of force constants betweens atoms with equal and opposite spin directions) and by deriving them for the prototype material system bcc Fe from first-principles calculations. In the paramagnetic regime, the two limits yield identical phonon spectra. Below the Curie temperature, however, there are regions in the parametric study that show qualitative differences, including a broadening of the phonon peaks. For bcc Fe, however, the quantitative modifications of phonon frequencies turn out to be small.

We combined experimental investigations and theoretical calculations to unveil an abnormal magnetic behavior caused by addition of the nonmagnetic element Cu in face-centered-cubic FeNiCoMn-based high-entropy alloys (HEAs). Upon Cu addition, the probed HEAs show an increase of both Curie temperature and saturation magnetization in as-cast and homogenized states. Specifically, the saturation magnetization of the as-cast HEAs at room temperature increases by 77% and 177% at a Cu content of 11 and 20 at. %, respectively, compared to the as-cast equiatomic FeNiCoMn HEA without Cu. The increase in saturation magnetization of the as-cast HEAs is associated with the formation of an Fe-Co rich phase in the dendritic regions. For the homogenized HEAs, the magnetic state at room temperature transforms from paramagnetism to ferromagnetism after 20 at. % Cu addition. The increase of the saturation magnetization and Curie temperature cannot be adequately explained by the formation of Cu enriched zones according to atom probe tomography analysis. Ab initio calculations suggest Cu plays a pivotal role in the stabilization of a ferromagnetic ordering of Fe, and reveal an increase of the Curie temperature caused by Cu addition which agrees well with the experimental results. The underlying mechanism behind this phenomenon lies in a combined change in unit-cell volume and chemical composition and the related energetic stabilization of the magnetic ordering upon Cu alloying as revealed by theoretical calculations. Thus, the work unveils the mechanisms responsible for the Cu effect on the magnetic properties of FeNiCoMn HEAs, and suggests that nonmagnetic elements are also crucial to tune and improve magnetic properties of HEAs.

The field of atomistic simulations of multicomponent materials and high entropy alloys is progressing rapidly, with challenging problems stimulating new creative solutions. In this Perspective, we present three topics that emerged very recently and that we anticipate will determine the future direction of research of high entropy alloys: the usage of machine-learning potentials for very accurate thermodynamics, the exploration of short-range order and its impact on macroscopic properties, and the more extensive exploitation of interstitial alloying and high entropy alloy surfaces for new technological applications. For each of these topics, we briefly summarize the key achievements, point out the aspects that still need to be addressed, and discuss possible future improvements and promising directions.