High-Pressure Induced Phase Transitions in High-Entropy Alloys: A Review
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paper_title: Nanostructured High‐Entropy Alloys with Multiple Principal Elements: Novel Alloy Design Concepts and Outcomes

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A new approach for the design of alloys is presented in this study. These high-entropy alloys with multi-principal elements were synthesized using well-developed processing technologies. Preliminary results demonstrate examples of the alloys with simple crystal structures, nanostructures, and promising mechanical properties. This approach may be opening a new era in materials science and engineering.
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paper_title: Microstructural development in equiatomic multicomponent alloys

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Abstract Multicomponent alloys containing several components in equal atomic proportions have been manufactured by casting and melt spinning, and their microstructures and properties have been investigated by a combination of optical microscopy, scanning electron microscopy, electron probe microanalysis, X-ray diffractrometry and microhardness measurements. Alloys containing 16 and 20 components in equal proportions are multiphase, crystalline and brittle both as-cast and after melt spinning. A five component Fe 20 Cr 20 Mn 20 Ni 20 Co 20 alloy forms a single fcc solid solution which solidifies dendritically. A wide range of other six to nine component late transition metal rich multicomponent alloys exhibit the same majority fcc primary dendritic phase, which can dissolve substantial amounts of other transition metals such as Nb, Ti and V. More electronegative elements such as Cu and Ge are less stable in the fcc dendrites and are rejected into the interdendritic regions. The total number of phases is always well below the maximum equilibrium number allowed by the Gibbs phase rule, and even further below the maximum number allowed under non-equilibrium solidification conditions. Glassy structures are not formed by casting or melt spinning of late transition metal rich multicomponent alloys, indicating that the confusion principle does not apply, and other factors are more important in promoting glass formation.
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paper_title: High-pressure studies with x-rays using diamond anvil cells.

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Pressure profoundly alters all states of matter. The symbiotic development of ultrahigh-pressure diamond anvil cells, to compress samples to sustainable multi-megabar pressures; and synchrotron x-ray techniques, to probe materials' properties in situ, has enabled the exploration of rich high-pressure (HP) science. In this article, we first introduce the essential concept of diamond anvil cell technology, together with recent developments and its integration with other extreme environments. We then provide an overview of the latest developments in HP synchrotron techniques, their applications, and current problems, followed by a discussion of HP scientific studies using x-rays in the key multidisciplinary fields. These HP studies include: HP x-ray emission spectroscopy, which provides information on the filled electronic states of HP samples; HP x-ray Raman spectroscopy, which probes the HP chemical bonding changes of light elements; HP electronic inelastic x-ray scattering spectroscopy, which accesses high energy electronic phenomena, including electronic band structure, Fermi surface, excitons, plasmons, and their dispersions; HP resonant inelastic x-ray scattering spectroscopy, which probes shallow core excitations, multiplet structures, and spin-resolved electronic structure; HP nuclear resonant x-ray spectroscopy, which provides phonon densities of state and time-resolved Mössbauer information; HP x-ray imaging, which provides information on hierarchical structures, dynamic processes, and internal strains; HP x-ray diffraction, which determines the fundamental structures and densities of single-crystal, polycrystalline, nanocrystalline, and non-crystalline materials; and HP radial x-ray diffraction, which yields deviatoric, elastic and rheological information. Integrating these tools with hydrostatic or uniaxial pressure media, laser and resistive heating, and cryogenic cooling, has enabled investigations of the structural, vibrational, electronic, and magnetic properties of materials over a wide range of pressure-temperature conditions.
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paper_title: Recent advances in high-pressure science and technology

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Abstract Recently we are witnessing the boom of high-pressure science and technology from a small niche field to becoming a major dimension in physical sciences. One of the most important technological advances is the integration of synchrotron nanotechnology with the minute samples at ultrahigh pressures. Applications of high pressure have greatly enhanced our understanding of the electronic, phonon, and doping effects on the newly emerged graphene and related 2D layered materials. High pressure has created exotic stoichiometry even in common Group 17, 15, and 14 compounds and drastically altered the basic σ and π bonding of organic compounds. Differential pressure measurements enable us to study the rheology and flow of mantle minerals in solid state, thus quantitatively constraining the geodynamics. They also introduce a new approach to understand defect and plastic deformations of nano particles. These examples open new frontiers of high-pressure research.
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paper_title: Calibration of the ruby pressure gauge to 800 kbar under quasi‐hydrostatic conditions

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An improved calibration curve of the pressure shift of the ruby R1 emission line was obtained under quasi-hydrostatic conditions in the diamond-window, high-pressure cell to 800 kbar. Argon was the pressure-transmitting medium. Metallic copper, as a standard, was studied in situ by X ray diffraction. The reference pressure was determined by calibration against known equations of state of the copper sample and by previously obtained data on silver.
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paper_title: The high-entropy alloys with high hardness and soft magnetic property prepared by mechanical alloying and high-pressure sintering

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Abstract The equiatomic multiprincipal CoCrFeCuNi and CoCrFeMnNi high-entropy alloys (HEAs) were consolidated via high pressure sintering (HPS) from the powders prepared by the mechanical alloying method (MA). The structures of the MA'ed CoCrFeCuNi and CoCrFeMnNi powders consisted of a face-centered-cubic (FCC) phase and a minority body-centered cubic (BCC) phase. After being consolidated by HPS at 5 GPa, the structure of both HEAs transformed to a single FCC phase. The grain sizes of the HPS'ed CoCrFeCuNi and CoCrFeMnNi HEAs were about 100 nm. The alloys keep the FCC structure until the pressure reaches 31 GPa. The hardness of the HPS'ed CoCrFeCuNi and CoCrFeMnNi HEAs were 494 Hv and 587 Hv, respectively, much higher than their counterparts prepared by casting. Both alloys show typical paramagnetism, however, possessing different saturated magnetization. The mechanisms responsible for the observed influence of Cu and Mn on mechanical behavior and magnetic property of the HEAs are discussed in detail.
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paper_title: Calculating elastic constants in high-entropy alloys using the coherent potential approximation: Current issues and errors

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The new class of high-entropy alloys (HEAs) materials have shown interesting properties, such as high strength and good ductility. However, HEAs present a great challenge for conventional ab initio calculations and the few available theoretical predictions involve a large degree of uncertainty. An often adopted theoretical tool to study HEAs from first-principles is based on the exact muffin-tin orbitals (EMTO) method in combination with the coherent potentials approximation (CPA), which can handle both chemical and magnetic disorders. Here we assess the performance of EMTO-CPA method in describing the elastic properties of HEAs based on Co, Cr, Fe, Mn, and Ni. We carefully scrutinize the effect of numerical parameters and the impact of various magnetic states on the calculated properties. The theoretical results for the elastic moduli are compared to the available experimental values.
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paper_title: Pressure-induced ordering phase transition in high-entropy alloy

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Abstract The order-disorder transition has long been viewed as an important key to study materials structures and properties. Especially, pressure-induced ordering attracted the intense research interest in the recent years. In the present work, the pressure-induced ordering phase transition (disordered-fcc to ordered-fcc structures) in a CoCrCuFeNiPr high-entropy alloy (HEA) was found by employing the in situ high-pressure energy-dispersive X-ray diffraction (EDXRD) technique. It is interesting to note that there exists a pressure-induced fast ordering transition at the pressure ranging from 7.8 GPa to 16.0 GPa, followed by a slow transition with the pressure increase up to 106.4 GPa. We suggest that this phenomenon is caused by the presence of some short-range-order (SRO) local structures in the CoCrCuFeNiPr HEA. These SRO structures can be regarded as embryos, which will develop into the ordered phase with increasing the pressure in the prototype materials. This pressure-induced ordering may provides a new technique for tuning structures and properties of HEAs.
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paper_title: Structural stability of high entropy alloys under pressure and temperature

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The stability of high-entropy alloys (HEAs) is a key issue before their selection for industrial applications. In this study, in-situ high-pressure and high-temperature synchrotron radiation X-ray diffraction experiments have been performed on three typical HEAs Ni20Co20Fe20Mn20Cr20, Hf25Nb25Zr25Ti25, and Re25Ru25Co25Fe25 (at. %), having face-centered cubic (fcc), body-centered cubic (bcc), and hexagonal close-packed (hcp) crystal structures, respectively, up to the pressure of ∼80 GPa and temperature of ∼1262 K. Under the extreme conditions of the pressure and temperature, all three studied HEAs remain stable up to the maximum pressure and temperatures achieved. For these three types of studied HEAs, the pressure-dependence of the volume can be well described with the third order Birch-Murnaghan equation of state. The bulk modulus and its pressure derivative are found to be 88.3 GPa and 4 for bcc-Hf25Nb25Zr25Ti25, 193.9 GPa and 5.9 for fcc-Ni20Co20Fe20Mn20Cr20, and 304.6 GPa and 3.8 for hcp-Re25Ru25Co25F...
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paper_title: Pressure-induced fcc to hcp phase transition in Ni-based high entropy solid solution alloys

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A pressure-induced phase transition from the fcc to a hexagonal close-packed (hcp) structure was found in NiCoCrFe solid solution alloy starting at 13.5 GPa. The phase transition is very sluggish and the transition did not complete at ∼40 GPa. The hcp structure is quenchable to ambient pressure. Only a very small amount (<5%) of hcp phase was found in the isostructural NiCoCr ternary alloy up to the pressure of 45 GPa and no obvious hcp phase was found in NiCoCrFePd system till to 74 GPa. Ab initio Gibbs free energy calculations indicated the energy differences between the fcc and the hcp phases for the three alloys are very small, but they are sensitive to temperature. The critical transition pressure in NiCoCrFe varies from ∼1 GPa at room temperature to ∼6 GPa at 500 K.
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paper_title: Temperature dependence of the mechanical properties of equiatomic solid solution alloys with face-centered cubic crystal structures

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We found that compared to decades-old theories of strengthening in dilute solid solutions, the mechanical behavior of concentrated solid solutions is relatively poorly understood. A special subset of these materials includes alloys in which the constituent elements are present in equal atomic proportions, including the high-entropy alloys of recent interest. A unique characteristic of equiatomic alloys is the absence of “solvent” and “solute” atoms, resulting in a breakdown of the textbook picture of dislocations moving through a solvent lattice and encountering discrete solute obstacles. Likewise, to clarify the mechanical behavior of this interesting new class of materials, we investigate here a family of equiatomic binary, ternary and quaternary alloys based on the elements Fe, Ni, Co, Cr and Mn that were previously shown to be single-phase face-centered cubic (fcc) solid solutions. The alloys were arc-melted, drop-cast, homogenized, cold-rolled and recrystallized to produce equiaxed microstructures with comparable grain sizes. Tensile tests were performed at an engineering strain rate of 10-3 s-1 at temperatures in the range 77–673 K. Unalloyed fcc Ni was processed similarly and tested for comparison. The flow stresses depend to varying degrees on temperature, with some (e.g. NiCoCr, NiCoCrMn and FeNiCoCr) exhibiting yield and ultimate strengths that increasemore » strongly with decreasing temperature, while others (e.g. NiCo and Ni) exhibit very weak temperature dependencies. Moreover, to better understand this behavior, the temperature dependencies of the yield strength and strain hardening were analyzed separately. Lattice friction appears to be the predominant component of the temperature-dependent yield stress, possibly because the Peierls barrier height decreases with increasing temperature due to a thermally induced increase of dislocation width. In the early stages of plastic flow (5–13% strain, depending on material), the temperature dependence of strain hardening is due mainly to the temperature dependence of the shear modulus. In all the equiatomic alloys, ductility and strength increase with decreasing temperature down to 77 K. Keywords« less
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paper_title: A Fracture-Resistant High-Entropy Alloy for Cryogenic Applications.

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A CrMnFeCoNi alloy is prepared by arc melting the elements and drop casting into copper molds, followed by cold forging and cross rolling at room temperature into sheets roughly 10 mm thick.
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paper_title: The influences of temperature and microstructure on the tensile properties of a CoCrFeMnNi high-entropy alloy

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Abstract An equiatomic CoCrFeMnNi high-entropy alloy, which crystallizes in the face-centered cubic (fcc) crystal structure, was produced by arc melting and drop casting. The drop-cast ingots were homogenized, cold rolled and recrystallized to obtain single-phase microstructures with three different grain sizes in the range 4–160 μm. Quasi-static tensile tests at an engineering strain rate of 10 −3 s −1 were then performed at temperatures between 77 and 1073 K. Yield strength, ultimate tensile strength and elongation to fracture all increased with decreasing temperature. During the initial stages of plasticity (up to ∼2% strain), deformation occurs by planar dislocation glide on the normal fcc slip system, {1 1 1}〈1 1 0〉, at all the temperatures and grain sizes investigated. Undissociated 1/2〈1 1 0〉 dislocations were observed, as were numerous stacking faults, which imply the dissociation of several of these dislocations into 1/6〈1 1 2〉 Shockley partials. At later stages (∼20% strain), nanoscale deformation twins were observed after interrupted tests at 77 K, but not in specimens tested at room temperature, where plasticity occurred exclusively by the aforementioned dislocations which organized into cells. Deformation twinning, by continually introducing new interfaces and decreasing the mean free path of dislocations during tensile testing (“dynamic Hall–Petch”), produces a high degree of work hardening and a significant increase in the ultimate tensile strength. This increased work hardening prevents the early onset of necking instability and is a reason for the enhanced ductility observed at 77 K. A second reason is that twinning can provide an additional deformation mode to accommodate plasticity. However, twinning cannot explain the increase in yield strength with decreasing temperature in our high-entropy alloy since it was not observed in the early stages of plastic deformation. Since strong temperature dependencies of yield strength are also seen in binary fcc solid solution alloys, it may be an inherent solute effect, which needs further study.
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paper_title: Ab initio thermodynamics of the CoCrFeMnNi high entropy alloy: Importance of entropy contributions beyond the configurational one

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We investigate the thermodynamic properties of the prototype equi-atomic high entropy alloy (HEA) CoCrFeMnNi by using finite-temperature ab initio methods. All relevant free energy contributions are considered for the hcp, fcc, and bcc structures, including electronic, vibrational, and magnetic excitations. We predict the paramagnetic fcc phase to be most stable above room temperature in agreement with experiment. The corresponding thermal expansion and bulk modulus agree likewise well with experimental measurements. A careful analysis of the underlying entropy contributions allows us to identify that the originally postulated dominance of the configurational entropy is questionable. We show that vibrational, electronic, and magnetic entropy contributions must be considered on an equal footing to reliably predict phase stabilities in HEA systems.
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paper_title: Irreversible Phase Transformation in a CoCrFeMnNi High Entropy Alloy under Hydrostatic Compression

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Abstract An equal-molar CoCrFeMnNi, face-centered-cubic high-entropy alloy system is investigated using in-situ angular-dispersive X-ray diffraction under hydrostatic compression up to 20 GPa via diamond anvil cell. The evolutions of multiple diffraction peaks are collected simultaneously to elucidate the phase stability field. The results indicated that an irreversible phase transformation had occurred in the high entropy alloy upon decompression to ambient pressure. A reference material (n-type silicon-doped gallium arsenide) was investigated following the same protocol to demonstrate the different deformation mechanisms. It is suggested that the atomic bonding characteristics on the phase stability may play an important role in the high entropy alloys.
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paper_title: Effects of non-hydrostaticity and grain size on the pressure-induced phase transition of the CoCrFeMnNi high-entropy alloy

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Recently, an irreversible polymorphic transition from face-centered cubic to hexagonal close-packing was surprisingly observed under high pressure in the prototype CoCrFeMnNi high-entropy alloys (HEAs) by various research groups. This unexpected phase transition brings new insights into the stability of HEAs, and its irreversibility stimulates exploration for new HEAs via high-pressure compression synthesis. However, the onset pressure for the phase transition was reported to fluctuate over a vast range from ∼7 to above 49 GPa in the reported experiments. The reason for this inconsistency remains unclear and puzzles the HEA community. To address this problem, this work systematically investigates the effects of non-hydrostaticity and grain size. Our results demonstrate that larger deviatoric stress induced by the non-hydrostaticity of the pressure medium and larger grain size of the initial sample can both promote a phase transition and, therefore, considerably depress the onset pressure.Recently, an irreversible polymorphic transition from face-centered cubic to hexagonal close-packing was surprisingly observed under high pressure in the prototype CoCrFeMnNi high-entropy alloys (HEAs) by various research groups. This unexpected phase transition brings new insights into the stability of HEAs, and its irreversibility stimulates exploration for new HEAs via high-pressure compression synthesis. However, the onset pressure for the phase transition was reported to fluctuate over a vast range from ∼7 to above 49 GPa in the reported experiments. The reason for this inconsistency remains unclear and puzzles the HEA community. To address this problem, this work systematically investigates the effects of non-hydrostaticity and grain size. Our results demonstrate that larger deviatoric stress induced by the non-hydrostaticity of the pressure medium and larger grain size of the initial sample can both promote a phase transition and, therefore, considerably depress the onset pressure.
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paper_title: High pressure synthesis of a hexagonal close-packed phase of the high-entropy alloy CrMnFeCoNi

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High-entropy alloys, near-equiatomic solid solutions of five or more elements, represent a new strategy for the design of materials with properties superior to those of conventional alloys. However, their phase space remains constrained, with transition metal high-entropy alloys exhibiting only face- or body-centered cubic structures. Here, we report the high-pressure synthesis of a hexagonal close-packed phase of the prototypical high-entropy alloy CrMnFeCoNi. This martensitic transformation begins at 14 GPa and is attributed to suppression of the local magnetic moments, destabilizing the initial fcc structure. Similar to fcc-to-hcp transformations in Al and the noble gases, the transformation is sluggish, occurring over a range of >40 GPa. However, the behaviour of CrMnFeCoNi is unique in that the hcp phase is retained following decompression to ambient pressure, yielding metastable fcc-hcp mixtures. This demonstrates a means of tuning the structures and properties of high-entropy alloys in a manner not achievable by conventional processing techniques.
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paper_title: Polymorphism in a high-entropy alloy

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Polymorphism, which describes the occurrence of different lattice structures in a crystalline material, is a critical phenomenon in materials science and condensed matter physics. Recently, configuration disorder was compositionally engineered into single lattices, leading to the discovery of high-entropy alloys and high-entropy oxides. For these novel entropy-stabilized forms of crystalline matter with extremely high structural stability, is polymorphism still possible? Here by employing in situ high-pressure synchrotron radiation X-ray diffraction, we reveal a polymorphic transition from face-centred-cubic (fcc) structure to hexagonal-close-packing (hcp) structure in the prototype CoCrFeMnNi high-entropy alloy. The transition is irreversible, and our in situ high-temperature synchrotron radiation X-ray diffraction experiments at different pressures of the retained hcp high-entropy alloy reveal that the fcc phase is a stable polymorph at high temperatures, while the hcp structure is more thermodynamically favourable at lower temperatures. As pressure is increased, the critical temperature for the hcp-to-fcc transformation also rises. Whether a polymorphic transition exists in high entropy alloys or not remains unclear since discovery of these alloys more than a decade ago. Here authors report an irreversible polymorphic transition fromfcc to hcp in the prototype FeCoCrMnNi high entropy alloy and provide evidence for fccphase being more stable than hcp phase only at high temperatures.
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paper_title: High-pressure high-temperature tailoring of High Entropy Alloys for extreme environments

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Abstract The exceptional performance of some High Entropy Alloys (HEAs) under extreme conditions holds out the possibility of new and exciting materials for engineers to exploit in future applications. In this work, instead of focusing solely on the effects of high temperature on HEAs, the effects of combined high temperature and high pressure were observed. Phase transformations occurring in a pristine HEA, the as-cast bcc–Al2CoCrFeNi, are heavily influenced by temperature, pressure, and by scandium additions. As-cast bcc–Al2CoCrFeNi and fcc–Al0.3CoCrFeNi HEAs are structurally stable below 60 GPa and do not undergo phase transitions. Addition of scandium to bcc–Al2CoCrFeNi results in the precipitation of hexagonal AlScM intermetallic (W-phase), which dissolves in the matrix after high-pressure high-temperature treatment. Addition of scandium and high-pressure sintering improve hardness and thermal stability of well-investigated fcc- and bcc- HEAs. The dissolution of the intermetallic in the main phase at high pressure suggests a new strategy in the design and optimization of HEAs.
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paper_title: Pressure-induced ordering phase transition in high-entropy alloy

paper_content:

Abstract The order-disorder transition has long been viewed as an important key to study materials structures and properties. Especially, pressure-induced ordering attracted the intense research interest in the recent years. In the present work, the pressure-induced ordering phase transition (disordered-fcc to ordered-fcc structures) in a CoCrCuFeNiPr high-entropy alloy (HEA) was found by employing the in situ high-pressure energy-dispersive X-ray diffraction (EDXRD) technique. It is interesting to note that there exists a pressure-induced fast ordering transition at the pressure ranging from 7.8 GPa to 16.0 GPa, followed by a slow transition with the pressure increase up to 106.4 GPa. We suggest that this phenomenon is caused by the presence of some short-range-order (SRO) local structures in the CoCrCuFeNiPr HEA. These SRO structures can be regarded as embryos, which will develop into the ordered phase with increasing the pressure in the prototype materials. This pressure-induced ordering may provides a new technique for tuning structures and properties of HEAs.
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paper_title: Structural stability of high entropy alloys under pressure and temperature

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The stability of high-entropy alloys (HEAs) is a key issue before their selection for industrial applications. In this study, in-situ high-pressure and high-temperature synchrotron radiation X-ray diffraction experiments have been performed on three typical HEAs Ni20Co20Fe20Mn20Cr20, Hf25Nb25Zr25Ti25, and Re25Ru25Co25Fe25 (at. %), having face-centered cubic (fcc), body-centered cubic (bcc), and hexagonal close-packed (hcp) crystal structures, respectively, up to the pressure of ∼80 GPa and temperature of ∼1262 K. Under the extreme conditions of the pressure and temperature, all three studied HEAs remain stable up to the maximum pressure and temperatures achieved. For these three types of studied HEAs, the pressure-dependence of the volume can be well described with the third order Birch-Murnaghan equation of state. The bulk modulus and its pressure derivative are found to be 88.3 GPa and 4 for bcc-Hf25Nb25Zr25Ti25, 193.9 GPa and 5.9 for fcc-Ni20Co20Fe20Mn20Cr20, and 304.6 GPa and 3.8 for hcp-Re25Ru25Co25F...
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paper_title: Effects of Al addition on the microstructure and mechanical property of AlxCoCrFeNi high-entropy alloys

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A five-component AlxCoCrFeNi high-entropy alloy (HEA) system with finely-divided Al contents (x in molar ratio, x = 0–2.0) was prepared by vacuum arc melting and casting method. The effects of Al addition on the crystal structure, microstructure and mechanical property were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), and Vickers hardness tester. The as-cast AlxCoCrFeNi alloys can possess face-centered cubic (FCC), body-centered cubic (BCC) or mixed crystal structure, depending on the aluminum content. The increase of aluminum content results in the formation of BCC structure which is a dominant factor of hardening. All the BCC phases in the as-cast alloys have a nano-scale two-phase structure formed by spinodal decomposition mechanism. The Al0.9CoCrFeNi alloy exhibits a finest spinodal structure consisting of alternating interconnected two-phase microstructure which explains its maximum hardness of Hv 527 among the alloys. The chemical composition analysis of FCC and BCC crystal structures, their lattice constants, overall hardness demonstrate that the formation of a single FCC solid solution should have Al addition <11 at.% and the formation of a single BCC solid solution requires Al addition at least 18.4 at.% in the AlxCoCrFeNi system.
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paper_title: Pressure-induced phase transition in the AlCoCrFeNi high-entropy alloy

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Abstract The recently discovered pressure-induced polymorphic transitions (PIPT) in high-entropy alloys (HEAs) have opened an avenue towards understanding the phase stability and achieving atomic structural tuning of HEAs. So far, whether there is any PIPT in the body-centered cubic ( bcc ) HEAs remains unclear. Here, we studied an ordered bcc -structured (B2 phase) AlCoCrFeNi HEA using in situ synchrotron radiation X-ray diffraction (XRD) up to 42 GPa and ex situ transmission electron microscopy, a PIPT to a likely-distorted phase was observed. These results highlight the effect of the lattice distortion on the stability of HEAs and extend the polymorphism into ordered bcc -structured HEAs.
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paper_title: Searching for Next Single-Phase High-Entropy Alloy Compositions

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There has been considerable technological interest in high-entropy alloys (HEAs) since the initial publications on the topic appeared in 2004. However, only several of the alloys investigated are truly single-phase solid solution compositions. These include the FCC alloys CoCrFeNi and CoCrFeMnNi based on 3d transition metals elements and BCC alloys NbMoTaW, NbMoTaVW, and HfNbTaTiZr based on refractory metals. The search for new single-phase HEAs compositions has been hindered by a lack of an effective scientific strategy for alloy design. This report shows that the chemical interactions and atomic diffusivities predicted from ab initio molecular dynamics simulations which are closely related to primary crystallization during solidification can be used to assist in identifying single phase high-entropy solid solution compositions. Further, combining these simulations with phase diagram calculations via the CALPHAD method and inspection of existing phase diagrams is an effective strategy to accelerate the discovery of new single-phase HEAs. This methodology was used to predict new single-phase HEA compositions. These are FCC alloys comprised of CoFeMnNi, CuNiPdPt and CuNiPdPtRh, and HCP alloys of CoOsReRu.
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paper_title: Structural stability of high entropy alloys under pressure and temperature

paper_content:

The stability of high-entropy alloys (HEAs) is a key issue before their selection for industrial applications. In this study, in-situ high-pressure and high-temperature synchrotron radiation X-ray diffraction experiments have been performed on three typical HEAs Ni20Co20Fe20Mn20Cr20, Hf25Nb25Zr25Ti25, and Re25Ru25Co25Fe25 (at. %), having face-centered cubic (fcc), body-centered cubic (bcc), and hexagonal close-packed (hcp) crystal structures, respectively, up to the pressure of ∼80 GPa and temperature of ∼1262 K. Under the extreme conditions of the pressure and temperature, all three studied HEAs remain stable up to the maximum pressure and temperatures achieved. For these three types of studied HEAs, the pressure-dependence of the volume can be well described with the third order Birch-Murnaghan equation of state. The bulk modulus and its pressure derivative are found to be 88.3 GPa and 4 for bcc-Hf25Nb25Zr25Ti25, 193.9 GPa and 5.9 for fcc-Ni20Co20Fe20Mn20Cr20, and 304.6 GPa and 3.8 for hcp-Re25Ru25Co25F...
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paper_title: High-Entropy Alloys in Hexagonal Close-Packed Structure

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The microstructures and properties of high-entropy alloys (HEAs) based on the face-centered cubic and body-centered cubic structures have been studied extensively in the literature, but reports on HEAs in the hexagonal close-packed (HCP) structure are very limited. Using an efficient strategy in combining phase diagram inspection, CALPHAD modeling, and ab initio molecular dynamics simulations, a variety of new compositions are suggested that may hold great potentials in forming single-phase HCP HEAs that comprise rare earth elements and transition metals, respectively. Experimental verification was carried out on CoFeReRu and CoReRuV using X-ray diffraction, scanning electron microscopy, and energy dispersion spectroscopy.
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paper_title: Pressure-induced phase transitions in HoDyYGdTb high-entropy alloy

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Abstract The HoDyYGdTb high-entropy alloy (HEA) was synthesized and its structural phase transitions were determined under compression up to 60.1 GPa at room temperature. Three transformations following the sequence hexagonal close-packed (hcp) → samarium type (Sm-type) → double hexagonal close-packed (dhcp) → distorted face-center cubic (dfcc) are observed at 4.4, 26.7, and 40.2 GPa, respectively. The high pressure equation of state was determined for the HEA according to third-order Birch-Murnaghan equation of state. The results show that the bulk modulus and atomic volume of the alloy obey the “additivity law”.
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paper_title: High-Entropy Alloys with a Hexagonal Close-Packed Structure Designed by Equi-Atomic Alloy Strategy and Binary Phase Diagrams

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High-entropy alloys (HEAs) with an atomic arrangement of a hexagonal close-packed (hcp) structure were found in YGdTbDyLu and GdTbDyTmLu alloys as a nearly single hcp phase. The equi-atomic alloy design for HEAs assisted by binary phase diagrams started with selecting constituent elements with the hcp structure at room temperature by permitting allotropic transformation at a high temperature. The binary phase diagrams comprising the elements thus selected were carefully examined for the characteristics of miscibility in both liquid and solid phases as well as in both solids due to allotropic transformation. The miscibility in interest was considerably narrow enough to prevent segregation from taking place during casting around the equi-atomic composition. The alloy design eventually gave candidates of quinary equi-atomic alloys comprising heavy lanthanides principally. The XRD analysis revealed that YGdTbDyLu and GdTbDyTmLu alloys thus designed are formed into the hcp structure in a nearly single phase. It was found that these YGdTbDyLu and GdTbDyTmLu HEAs with an hcp structure have delta parameter (δ) values of 1.4 and 1.6, respectively, and mixing enthalpy (ΔHmix) = 0 kJ/mol for both alloys. These alloys were consistently plotted in zone S for disordered HEAs in a δ-ΔHmix diagram reported by Zhang et al. (Adv Eng Mater 10:534, 2008). The value of valence electron concentration of the alloys was evaluated to be 3 as the first report for HEAs with an hcp structure. The finding of HEAs with the hcp structure is significant in that HEAs have been extended to covering all three simple metallic crystalline structures ultimately followed by the body- and face-centered cubic (bcc and fcc) phases and to all four simple solid solutions that contain the glassy phase from high-entropy bulk metallic glasses.
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paper_title: Rare-earth high entropy alloys with hexagonal close-packed structure

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The formation of octonary DyErGdHoLuScTbY and senary DyGdHoLaTbY and ErGdHoLaTbY high-entropy alloys (HEAs) with the hexagonal close-packed (HCP) structure was reported in this study. Experiments using scanning electron microscopy and x-ray diffraction confirmed the single HCP solid solution in the as-cast state for these three HEAs if the presence of minor rare-earth oxides due to contamination from processing is ignored. The measured compressive yield stress values for these HEAs at room temperature are 245, 205, and 360 MPa for the ErGdHoLaTbY, DyGdHoLaTbY, and DyErGdHoLuScTbY HEAs, respectively. The corresponding solid solution strengthening contributions for these HEAs were estimated using a simple elastic model, and the resulting contributions were 28 MPa, 27 MPa, and 42 MPa for the three aforementioned HEAs.The formation of octonary DyErGdHoLuScTbY and senary DyGdHoLaTbY and ErGdHoLaTbY high-entropy alloys (HEAs) with the hexagonal close-packed (HCP) structure was reported in this study. Experiments using scanning electron microscopy and x-ray diffraction confirmed the single HCP solid solution in the as-cast state for these three HEAs if the presence of minor rare-earth oxides due to contamination from processing is ignored. The measured compressive yield stress values for these HEAs at room temperature are 245, 205, and 360 MPa for the ErGdHoLaTbY, DyGdHoLaTbY, and DyErGdHoLuScTbY HEAs, respectively. The corresponding solid solution strengthening contributions for these HEAs were estimated using a simple elastic model, and the resulting contributions were 28 MPa, 27 MPa, and 42 MPa for the three aforementioned HEAs.
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paper_title: First hexagonal close packed high-entropy alloy with outstanding stability under extreme conditions and electrocatalytic activity for methanol oxidation

paper_content:

Abstract High-entropy alloys containing 5 and 6 platinum group metals have been prepared by thermal decomposition of single-source precursors non requiring high temperature or mechanical alloying. The prepared Ir 0.19 Os 0.22 Re 0.21 Rh 0.20 Ru 0.19 alloy is the first example of a single-phase hexagonal high-entropy alloy. Heat treatment up to 1500 K and compression up to 45 GPa do not result in phase changes, a record temperature and pressure stability for a single-phase high-entropy alloy. The alloys show pronounced electrocatalytic activity in methanol oxidation, which opens a route for the use of high-entropy alloys as materials for sustainable energy conversion.
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paper_title: Density functional theory based calculations for high pressure research

paper_content:

Abstract Density functional theory based calculations are commonly employed to complement experimental high pressure research. Here, a brief overview of the underlying theory and available codes is provided, followed by some applications. The influence of the choice of the exchange-correlation functional on predicted structural parameters and physical properties is discussed.
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paper_title: Ab initio thermodynamics of the CoCrFeMnNi high entropy alloy: Importance of entropy contributions beyond the configurational one

paper_content:

We investigate the thermodynamic properties of the prototype equi-atomic high entropy alloy (HEA) CoCrFeMnNi by using finite-temperature ab initio methods. All relevant free energy contributions are considered for the hcp, fcc, and bcc structures, including electronic, vibrational, and magnetic excitations. We predict the paramagnetic fcc phase to be most stable above room temperature in agreement with experiment. The corresponding thermal expansion and bulk modulus agree likewise well with experimental measurements. A careful analysis of the underlying entropy contributions allows us to identify that the originally postulated dominance of the configurational entropy is questionable. We show that vibrational, electronic, and magnetic entropy contributions must be considered on an equal footing to reliably predict phase stabilities in HEA systems.
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paper_title: Perspective: crystal structure prediction at high pressures.

paper_content:

Crystal structure prediction at high pressures unbiased by any prior known structure information has recently become a topic of considerable interest. We here present a short overview of recently developed structure prediction methods and propose current challenges for crystal structure prediction. We focus on first-principles crystal structure prediction at high pressures, paying particular attention to novel high pressure structures uncovered by efficient structure prediction methods. Finally, a brief perspective on the outstanding issues that remain to be solved and some directions for future structure prediction researches at high pressure are presented and discussed.
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paper_title: Materials discovery at high pressures

paper_content:

High pressure offers a unique degree of freedom for the creation of new materials, leading to new superconductors, superhard materials, high-energy-density materials and exotic chemical materials with unprecedented properties. This Review discusses these materials, along with recently developed theoretical and experimental methods for materials discovery at high pressures.
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paper_title: A critical review of high entropy alloys and related concepts

paper_content:

Abstract : High entropy alloys (HEAs) are barely 12 years old. The field has stimulated new ideas and has inspired the exploration of the vast composition space offered by multi-principal element alloys (MPEAs). Here we present a critical review of this field, with the intent of summarizing key findings, uncovering major trends and providing guidance for future efforts. Major themes in this assessment include definition of terms; thermodynamic analysis of complex, concentrated alloys (CCAs); taxonomy of current alloy families; microstructures; mechanical properties; potential applications; and future efforts. Based on detailed analyses, the following major results emerge. Although classical thermodynamic concepts are unchanged, trends in MPEAs can be different than in simpler alloys. Common thermodynamic perceptions can be misleading and new trends are described. From a strong focus on 3d transition metal alloys, there are now seven distinct CCA families. A new theme of designing alloy families by selecting elements to achieve a specific, intended purpose is starting to emerge. A comprehensive microstructural assessment is performed using three datasets: experimental data drawn from 408 different alloys and two computational datasets generated using the CALculated PHAse Diagram (CALPHAD) method. Each dataset emphasizes different elements and shows different microstructural trends. Trends in these three datasets are all predicted by a structure in - structure out (SISO) analysis developed here that uses the weighted fractions of the constituent element crystal structures in each dataset. A total of 13 distinct multi-principal element single-phase fields are found in this microstructural assessment. Relationships between composition, microstructure and properties are established for 3d transition metal MPEAs, including the roles of Al, Cr and Cu. Critical evaluation shows that commercial austenitic stainless steels and nickel alloys with 3 or more principal elements are MPEAs.
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Title: High-Pressure Induced Phase Transitions in High-Entropy Alloys: A Review

Section 1: Introduction
Description 1: Introduce the concept of high-entropy alloys (HEAs) and their significance in material science. Mention the discovery of single solid-solution phase alloys with multi-principal elements and the resulting focus on high-entropy alloys.

Section 2: Experimental Methods
Description 2: Detail the experimental techniques used to study high-entropy alloys under high pressure, with a focus on diamond anvil cells (DACs) and in situ measurement techniques.

Section 3: Structural Stability and Evolution of HEAs under High Pressure
Description 3: Review the structural stability of high-entropy alloys under high pressure based on recent research. Discuss different initial crystal structures and their transitions.

Section 4: Fcc-Structured HEAs
Description 4: Highlight findings specific to fcc-structured high-entropy alloys, including phase transition behaviors and the effects of various factors like pressure environment, grain size, and alloying elements.

Section 5: Bcc-Structured HEAs
Description 5: Discuss the structural stability of bcc-structured high-entropy alloys under high pressure, including specific examples and any observed phase transitions.

Section 6: Hcp-Structured HEAs
Description 6: Provide an overview of high-pressure stability in hcp-structured high-entropy alloys, with specific cases and observed phase transitions during compression experiments.

Section 7: Conclusions and Outlooks
Description 7: Summarize the key findings from high-pressure studies on high-entropy alloys. Provide future outlooks for research directions, including synergic effects of pressure-composition-temperature, combining high-pressure techniques, and theoretical calculations.