Presence Of Short-range Order Research Articles

Platinum-Group Metal High-Entropy Selenides for the Hydrogen Evolution Reaction.

The selenides of platinum-group metals (PGMs) are emerging as promising catalysts for diverse electrochemical reactions. To date, most studies have focused on single metal or bimetallic systems, whereas the preparation of a high-entropy (HE) selenide consisting of five or more PGM elements holds the promise to further enhance catalytic performance by introducing abundant active sites with various local coordination environments and electronic structures. Herein, we report for the first time the synthesis of PGM-based HE-Selenide (HE-Se) nanoparticles with a unique amorphous structure. The atomic metal-Se coordination and the presence of short-range order were thoroughly revealed. It is further shown that the amorphous HE-Se can be facilely transformed into a single-phase crystalline HE-Se with a cubic structure by thermal annealing. Catalytically, the amorphous HE-Se showed better acidic hydrogen evolution activity over monometallic PGM-based selenides and the crystalline counterpart, demonstrating the advantages of high-entropy configuration and amorphous structure. Our findings may pave the way toward the synthesis and property exploration of amorphous PGM-based selenides with tunable compositions.

Comprehensive Investigation of the Crystal Structure of Cation-Disordered Li3VO4 as a High-Rate Anode Material: Unveiling the Dichotomy between Order and Disorder.

This study investigates mechanochemical synthesis and cation-disordering mechanism of wurtzite-type Li3VO4 (LVO), highlighting its promise as a high-performance anode material for lithium-ion batteries and hybrid supercapacitors. Mechanochemical treatment of pristine LVO using a high-energy ball mill results in a "pure cation-disordered" LVO phase, allowing for meticulous analysis of cation arrangement. The X-ray and neutron diffraction study demonstrates progressive loss of order in LVO crystal with increasing milling duration. High-resolution transmission electron microscopy reveals disrupted lattice fringes, indicating cationic misalignment. Pair-distribution function analysis confirms loss of cation arrangements and the presence of short-range order. Combination of these multiple analytical techniques achieves a comprehensive understanding of cation regularity and clearly demonstrates order/disorder dichotomy in cation-disordered materials, ranging from short (<8 Å) to middle-long range (8-30 Å), using an integrated superstructure model of the cation-disordered LVO crystals. Electrochemical testing reveals that mechanochemically treated LVO exhibits superior rate capability, with a 70% capacity retention at a high current density of 50C-rate. Lithium diffusion coefficient measurements demonstrate enhanced lithium-ion mobility in the mechanochemically treated LVO, attributed to cation-disordering effect. These findings provide valuable insights into mechanochemical cation-disordering in LVO, presenting its potential as an efficient anode material for lithium-ion-based electrochemical energy storage.

Tuning chemical short-range order for simultaneous strength and toughness enhancement in NiCoCr medium-entropy alloys

The pursuit of enhancing strength and toughness remains a critical endeavor in the field of structural materials. This study explores two distinct strategies to overcome the traditional strength-toughness trade-off. Specifically, we manipulate the chemical composition and short-range order (SRO) of the NiCoCr medium-entropy alloy, which has shown remarkable fracture toughness in recent experiments. Utilizing molecular dynamics simulations, we uncover nano-scale deformation mechanisms during crack propagation. Our findings highlight that optimizing the SRO degree leads to improvements in both atomic scale strength and toughness defined as the area underneath stress-strain curves from MD simulations. In contrast, a trade-off between strength and toughness persists when only manipulating the Ni content in the NiCoCr alloy. Based on the simulation results, we establish a strong correlation between toughness, strength, surface energies, and unstable stacking fault energies. These factors are influenced by the chemical composition and SROs in NiCoCr, with SROs acting as strong obstacles to dislocations, thereby contributing to additional strength. The exceptional toughness of NiCoCr with SRO arises from a synergy of intrinsic and extrinsic mechanisms, including dislocation glide, nanobridging during nanovoid coalescence and zigzag crack path. It is found that, in the presence of SRO, intrinsic toughening mechanisms usually associated with crack tip blunting and dissipation can also facilitate the onset of extrinsic toughening mechanisms of nanobridging and zig-zag crack path associated with nanovoid formation and coalescence. This study emphasizes the importance of tailoring SRO in designing materials with enhanced strength and toughness.

Cu–Mg dilute alloys- Assessment of strengthening, internal friction, and electrical conductivity

Overcoming the strength-conductivity trade-off has long been an issue for commercial copper alloys. However, a synergy between strength and electrical conductivity can be achieved by reasonable adjustment of the microstructure. It is known that the formation of Short-Range Order (SRO) in a solid solution can change the mechanical and electrical behavior of the materials. Currently, the prediction of SRO formation is widely based on computational techniques. In the present study, Miedema's thermodynamical approach is applied for the assessment of alloying elements' potential to form SRO in the copper lattice. According to this methodology, magnesium tends to form SRO with copper. The mechanical, electrical, and structural properties of the oxygen-free copper (Cu-OFC), Cu–Mg0.14 wt%, and Cu–Mg0.50 wt% strips fabricated by continuous extrusion forming process (Conform) have been investigated. According to the optical microscopy investigations, the average grain sizes of the Mg alloyed samples were observed to be lower compared to that of OFC. The Vickers hardness measurements were carried out and the hardness values for Cu-OFC, Cu–Mg0.14, and Cu–Mg0.50 samples were recorded as 56.3 HV, 76.05 HV, and 87.68 HV, and the yield strengths as 80, 150 and 260 MPa, respectively. A decrement in electrical conductivity was observed with the increasing Mg addition. Dynamic elastic modulus test measurements, which refer to internal friction, have been performed by impulse excitation technique to elucidate the presence of SRO in the dilute Cu–Mg systems. The anomalous “bump” formation in the temperature-elastic modulus profiles of the Cu–Mg samples was remarkable which has been attributed to the SRO formation.

Revealing the deformation mechanisms of 〈110〉 symmetric tilt grain boundaries in CoCrNi medium-entropy alloy

The synergy of multiple deformation mechanisms responsible for the excellent mechanical properties attracts an increasing interest in CoCrNi medium entropy alloy (MEA). In this study, we employed molecular dynamics simulations to investigate the chemical properties of grain boundaries (GBs) and their influence on deformation mechanisms in CrCoNi MEA, with particular emphasis on role of lattice distortion and short-range order (SRO) in dislocation plasticity. After aging, we found Ni element segregate at GB through short-range diffusion driven by a more negative segregation enthalpy. The degree of SRO within the GB region is significantly correlated with the Ni concentration, and it markedly influences the structure and local stress distribution of the GB. Compared to the lattice distortion, SRO can effectively suppress the GB dislocations nucleation and slip, thereby increasing yield strength of the material. During the plastic stage, although the deformation microstructure is intimately linked to the active slip systems and grain orientation, the presence of SRO, as well as the resultant rugged dislocation pathways and increased slip resistance lowers the propensity for stacking faults and phase transformation. The current findings can enhance a fundamental comprehension of diverse deformation mechanisms in CoCrNi MEA and suggest that the chemical characteristics of GB could serve as a pivotal approach for modifying the mechanical properties of MEAs.

On the origin of diffuse intensities in fcc electron diffraction patterns.

Interpreting diffuse intensities in electron diffraction patterns can be challenging in samples with high atomic-level complexity, as often is the case with multi-principal element alloys. For example, diffuse intensities in electron diffraction patterns from simple face-centred cubic (fcc) and related alloys have been attributed to short-range order1, medium-range order2 or a variety of different {111} planar defects, including thin twins3, thin hexagonal close-packed layers4, relrod spiking5 and incomplete ABC stacking6. Here we demonstrate that many of these diffuse intensities, including [Formula: see text]{422} and [Formula: see text]{311} in ⟨111⟩ and ⟨112⟩ selected area diffraction patterns, respectively, are due to reflections from higher-order Laue zones. We show similar features along many different zone axes in a wide range of simple fcc materials, including CdTe, pure Ni and pure Al. Using electron diffraction theory, we explain these intensities and show that our calculated intensities of projected higher-order Laue zone reflections as a function of deviation from their Bragg conditions match well with the observed intensities, proving that these intensities are universal in these fcc materials. Finally, we provide a framework for determining the nature and location of diffuse intensities that could indicate the presence of short-range order or medium-range order.

Effect of short-range order on the high-temperature plastic deformation behavior of Ni–Cr–W, Ni–W, and Ni–Re single crystals

The development of a Ni-based superalloy that consists of only the γ-solid-solution phase is highly desired for some applications such as high-temperature gas-cooled reactors in power plants. In this study, the temperature dependence of the plastic deformation behavior of Ni–22Cr–8W (at%) alloy was examined for the first time by using a single crystal, focusing on the influence of the short-range order (SRO), especially upon high-temperature deformation behavior. The critical resolved shear stress (CRSS) for (111)[101¯] slip exhibited a rapid decrease as the temperature increased at low temperatures but an almost constant value of ∼45 MPa between 500 and 900 °C. In addition, a slight yield stress anomaly (YSA) was observed, reaching a maximum value at 1000 °C.To clarify the influence of the SRO on the YSA behavior, the mechanical properties of Ni–8W and Ni–5Re single crystals were also examined. Similar temperature dependence for the CRSS, including the occurrence of slight YSA, was observed for Ni–8W, in which SRO developed. In the Ni–5Re single crystal in which SRO did not significantly develop, however, the CRSS monotonically decreased as the temperature increased. The results suggest that the presence of SRO in a Ni–Cr–W alloy contributes to the strengthening of the alloy not only at low temperatures but also at high temperatures up to ∼1000 °C. The results strongly suggested that the pseudo-PLC effect is related to the origin of YSA appearing in Ni-based γ-solid-solution alloys at high temperatures.

Short-range order and its impacts on the BCC MoNbTaW multi-principal element alloy by the machine-learning potential

We utilize a machine-learning force field, trained by a neural network (NN) with bispectrum coefficients as descriptors, to investigate the chemical short-range order (SRO) influences on the BCC MoNbTaW alloy strengthening mechanism. The NN interatomic potential offers a transferable force field that exhibits accuracy comparable to density functional theory. This innovative NN potential is employed to examine the SRO effects on various aspects such as elasticity, vibrational modes, plasticity, and strength in the MoNbTaW multi-principal element alloy (MPEA). The findings reveal a significant attraction between Mo-Ta pairs, resulting in the formation of locally ordered B2 clusters. These clusters can be adjusted via temperature and enhanced by Nb content. The presence of SRO leads to an increase in high-frequency phonon modes and introduces additional lattice friction to dislocation motion. This approach facilitates efficient compositional screening, paving the way for computational-guided materials design of novel MPEAs with enhanced performance. Furthermore, it opens up avenues for tuning the mechanical properties through optimization of the processing parameters.

Dislocation plasticity in equiatomic NiCoCr alloys: Effect of short-range order

Equiatomic NiCoCr solid solutions have been shown by recent experiments and atomistic simulations to display exceptional mechanical properties that have been suggested to be linked to nanostructural short-range order (SRO) features that may arise from thermal treatments, such as annealing or/and aging. Here we use hybrid Monte Carlo--molecular dynamics simulations to gain further insights of thermal effects on the SRO formation as well as the edge dislocation plasticity mechanisms of equiatomic NiCoCr face-centered cubic solid solution. For that purpose, we utilize two well-known NiCoCr interatomic potentials, one of which displays well-documented SRO, believed to be linked to experimental evidence and labeled as the Li-Sheng-Ma potential, while the other (Farkas-Caro) does not. We use these two potentials to discern short-range ordering (from inherent randomness in random solid solutions) and understand how SROs influence dislocation depinning dynamics in various thermal annealing scenarios. In this context, we used robust, scale-dependent metrics to infer a characteristic SRO size in the Li-Sheng-Ma case by probing local concentration fluctuations which otherwise indicate uncorrelated patterns in the Farkas-Caro case in a close agreement with random alloys. Our Voronoi-based analysis shows meaningful variations of local misfit properties owing to the presence of SROs. Using relevant order parameters, we also report on the drastic increase of chemical ordering within the stacking fault region. More importantly, we find that the Li-Sheng-Ma potential leads to excellent edge dislocation depinning strength with low stacking fault width. Our findings indicate an enhanced roughening mechanism due to the SROs-misfit synergy that leads to significant improvements in dislocation glide resistance. We argue that the improvements in alloy strength have their atomistic origins in the interplay between nanoscopic SROs and atomic-level misfit properties.

Effects of short-range order on phase equilibria and opto-electronic properties of ternary alloy ZnxCd1-xTe

We employ first principles methods based on density functional theory and beyond to study ZnxCd1-xTe, 0≤x≤1, alloys in the zinc blende (B3) crystal structure. Cluster Expansion and Monte Carlo formalisms were deployed to provide a phase diagram determining consolute temperature of 387 K at 40% Zn concentration. Opto-electronic properties are computed with the hybrid HSE06 functional for disordered ZnxCd1-xTe alloys, which were simulated using special quasi-random structures. Bowing effects in the bandgap and effective carrier masses were observed in alloying which can be attributed to local geometrical distortions as portrayed by bond length distributions. Downward bowing in the electronic bandgap will be beneficial in photovoltaic applications through increased net photocurrent. Absorption coefficients show robust absorption in ZnxCd1-xTe as indicated by substantial optical absorption throughout all Zn concentrations, aided by low reflectivity that ensures a high absorption. Presence of short-range order in Zn0.25Cd0.75Te was observed through clustering and anti-clustering among different cationic species of Zn and Cd. It has a value of 0.11 at 1000 K compared to −0.79 at 400 K. The bandgap of Zn0.25Cd0.75Te at 1000 K was found to be slightly higher, 0.05 eV, than at 400 K, consistent with the value of short-range order. Thus, short-range order and possibly composition can be used in the design and synthesis of the appropriate solar cell, thereby improving the performance in this system.

Maximum strength and dislocation patterning in multi-principal element alloys.

Multi-principal element alloys (MPEAs) containing three or more components in high concentrations render a tunable chemical short-range order (SRO). Leveraging large-scale atomistic simulations, we probe the limit of Hall-Petch strengthening and deformation mechanisms in a model CrCoNi alloy and unravel chemical ordering effects. The presence of SRO appreciably increases the maximum strength and lowers the propensity for faulting and structure transformation, accompanied by intensification of planar slip and strain localization. Deformation grains exhibit notably different microstructures and dislocation patterns that prominently depend on their crystallographic orientation and the number of active slip planes. Grain of single-planar slip attains the highest volume fraction of deformation-induced structure transformation, and grain with double-slip planes develops the densest dislocation network. These results advancing the fundamental understanding of deformation mechanisms and dislocation patterning in MPEAs suggest a mechanistic strategy for tuning mechanical behavior through simultaneously tailoring grain texture and local chemical order.

On the deformation behavior of CoCrNi medium entropy alloys: Unraveling mechanistic competition

Recently, CoCrNi medium entropy alloys (MEA) have been the subject of numerous investigations due to their unique mechanical properties such as an exceptionally high strength-ductility combination. The resulting superior toughness of CoCrNi MEAs is attributed to an interplay of multiple deformation mechanisms, such as twinning, and partial and perfect dislocation glide. The current understanding of MEA deformation mostly stems from an indirect analysis of the defect evolution in deformed microstructures, where the contributions of individual mechanisms are assessed from the relative concentrations of associated defect structures. Here, we propose that the mechanistic contributions to microstructural deformation are more properly reflected by the percentages of total strain accommodation. Using atomistic simulations, the mechanical response of nanocrystalline CoCrNi MEA under uniaxial tension is investigated as function of grain size and chemical short-range ordering (SRO). The contributions of deformation mechanisms are resolved directly from the amount of strain accommodation by leveraging continuum based kinematic metrics. It is found that during initial loading, deformation occurs by partial dislocation slip, in agreement with experimental observations. Under continued loading, the governing deformation mechanisms transition to twinning and perfect dislocation slip. Furthermore, the grain size that corresponds to the maximum strength is found to decrease in presence of SRO.

Retainable short-range order effects on the strength and toughness of NbMoTaW refractory high-entropy alloys

Short range order (SRO) can affect the dislocation glide and twin nucleation in high-entropy alloys (HEAs), leading to varying mechanical performance. However, the mechanical implications of SRO in refractory HEAs (RHEAs) remain largely unknown due to the lack of understanding of the nanoscale deformation. Here, the role of SRO on the tensile mechanical properties of single crystal equiatomic NbMoTaW RHEAs is investigated using the hybrid Monte Carlo method and molecular dynamics simulation. We find that the presence of SRO can simultaneously enhance the strength and toughness over a wide range of temperatures under very fast strain rate. The enhancement is larger at lower temperature due to higher degree of SRO. The effects of SRO strengthening and toughening are retainable after unloading from the plastic stage, due to the unexpected twinning-assisted pseudo-elastic deformation. The fundamental principles of SRO are provided to facilitate the rational design and applications of RHEAs.

Short-range order localizing diffusion in multi-principal element alloys

The impact of chemical short-range order (SRO) on diffusion is computationally studied and theoretically analyzed in two classes of multi-principal elements alloys, fcc CrCoNi and bcc MoNbTa. We find the presence of SRO considerably reduces and localizes vacancy-mediated diffusion. The diffusivity reduction is induced by an increase of migration barrier (decreasing jump frequency) and enhanced diffusion correlation that lowers the effectiveness of atomic jumps. By sampling the diffusion pathways and associated energy barriers, a picture of SRO-stretched potential energy landscape is conceived that elucidates an increasing backward jumps and vacancy trapping effect stemming from chemical ordering. The results imply controlling the ordering in chemistry can act as a potential approach for manipulating diffusional behaviors in multi-principal elements alloys.

Atomistic simulations of dislocation mobility in refractory high-entropy alloys and the effect of chemical short-range order

Refractory high-entropy alloys (RHEAs) are designed for high elevated-temperature strength, with both edge and screw dislocations playing an important role for plastic deformation. However, they can also display a significant energetic driving force for chemical short-range ordering (SRO). Here, we investigate mechanisms underlying the mobilities of screw and edge dislocations in the body-centered cubic MoNbTaW RHEA over a wide temperature range using extensive molecular dynamics simulations based on a highly-accurate machine-learning interatomic potential. Further, we specifically evaluate how these mechanisms are affected by the presence of SRO. The mobility of edge dislocations is found to be enhanced by the presence of SRO, whereas the rate of double-kink nucleation in the motion of screw dislocations is reduced, although this influence of SRO appears to be attenuated at increasing temperature. Independent of the presence of SRO, a cross-slip locking mechanism is observed for the motion of screws, which provides for extra strengthening for refractory high-entropy alloy system.

Local Ordering Tendency in Body-Centered Cubic (BCC) Multi-Principal Element Alloys

The recent development of high-entropy alloys (HEAs) has opened a new avenue for alloy design by incorporating multiple principal elements into a simple crystal lattice. In HEAs, short-range chemical ordering may arise due to the different mixing properties of various constituent elements. In this work, we explore the trend of elemental arrangement in five typical body-centered cubic (BCC) multi-principal element alloys (MPEAs), including CrFeV, HfNbZr, TaVW, NbTaV, and TaTiV. Combining the Monte Carlo method and density-functional theory calculations, we calculated the evolution of short-range order (SRO) parameters in these alloys at 500 K. Our results demonstrated that all these MPEAs might develop a certain degree of SRO, depending on the mixing properties of different element pairs. Using a modified quasi-chemical model, we show that the SRO values in these MPEAs can be accurately predicted as long as the mixing enthalpy values between different atomic pairs are known. The presence of SRO has a profound impact on the local structure of MPEAs, which further alters the electronic and elastic properties of MPEAs. Our results provide a theoretical understanding of the basic alloy structure of novel MPEAs, which is an essential step toward tailoring their properties.

Ab initio modeling of the energy landscape for screw dislocations in body-centered cubic high-entropy alloys

In traditional body-centered cubic (bcc) metals, the core properties of screw dislocations play a critical role in plastic deformation at low temperatures. Recently, much attention has been focused on refractory high-entropy alloys (RHEAs), which also possess bcc crystal structures. However, unlike face-centered cubic high-entropy alloys (HEAs), there have been far fewer investigations into bcc HEAs, specifically on the possible effects of chemical short-range order (SRO) in these multiple principal element alloys on dislocation mobility. Here, using density functional theory, we investigate the distribution of dislocation core properties in MoNbTaW RHEAs alloys, and how they are influenced by SRO. The average values of the core energies in the RHEA are found to be larger than those in the corresponding pure constituent bcc metals, and are relatively insensitive to the degree of SRO. However, the presence of SRO is shown to have a large effect on narrowing the distribution of dislocation core energies and decreasing the spatial heterogeneity of dislocation core energies in the RHEA. It is argued that the consequences of the mechanical behavior of HEAs is a change in the energy landscape of the dislocations, which would likely heterogeneously inhibit their motion.

Study of short range correlations and two-fold spin reorientation in NdFe0.5Mn0.5O3

Detailed powder neutron diffraction studies as a function of temperature is performed on NdFe0.5Mn0.5O3 in the temperature range 400–1.5 K. Diffused magnetic scattering is observed due to three dimensional short range ordering (SRO), between Fe3+/Mn3+ spins, over the whole temperature range 400–1.5 K. The presence of SRO is independent of long range ordering (LRO) in this compound which has never been observed in any Fe3+/Mn3+ based compounds. Further, in this compound two-fold spin reorientation is discussed in the temperature range 300–1.5 K. Development of long range ordering at 300 K is due to the mixture of Γ4 and Γ1 magnetic structure, not like other orthoferrites which have Γ4 structure at 300 K. This occurs due to the presence of large single ion anisotropy of Mn3+ ions. Volume fraction of Γ4 decreases with temperature leading to pure Γ1 magnetic structure in the temperature range 150–90 K. Another spin reorientation of Fe3+/Mn3+ spins occurs from Γ1 to Γ2 in the temperature range 70–25 K.

High temperature dielectric investigation, optical and conduction properties of GdFe0.5Cr0.5O3 perovskite

The present study reports the synthesis of GdFe0.5Cr0.5O3 by a conventional solid-state reaction route and the investigation of its structural, morphological, and optical properties. Dielectric and electric behaviors as a function of both high temperature and frequency are also presented. GdFe0.5Cr0.5O3 crystallizes in a Pbnm orthorhombic cell with an average grain size of 670 nm. The Mössbauer spectrum at room temperature shows the existence of Fe3+ in an octahedral symmetry with the presence of short-range order between the antiferromagnetic and the paramagnetic states. An optical study reveals a direct bandgap with an energy of about Eg=1.87eV. The dielectric relaxation is explained based on the Maxwell–Wagner polarization mechanism asserted to be arising in the interfaces of grains and grain boundaries. The charge carrier hopping is assumed to be along the (Fe,Cr)3+–VO∙–(Fe,Cr)2+ chain. A high temperature dielectric study is performed between 298 and 800 K, revealing successive transitions presumed to be associated with magnetic and electric ordering. The conduction mechanism is provided by the correlated barrier hopping model, while the ac-conductivity, at high temperatures, is dominated by oxygen vacancy motion.

Local order in Cr-Fe-Co-Ni: Experiment and electronic structure calculations

A quenched-in state of thermal equilibrium (at 723 K) in a single crystal of Cr-Fe-Co-Ni close to equal atomic percent was studied. Atom probe tomography revealed a single-phase state with no signs of long-range order. The presence of short-range order (SRO) was established by diffuse x-ray scattering exploiting the variation in scattering contrast close to the absorption edges of the constituents: At the incoming photon energies of 5969, 7092, and 8313 eV, SRO maxima that result from the linear superposition of the six partial SRO scattering patterns, were always found at $X$ position. Electronic structure calculations showed that this type of maximum stems from the strong Cr-Ni and Cr-Co pair correlations, that are furthermore connected with the largest scattering contrast at 5969 eV. The calculated effective pair interaction parameters revealed an order-disorder transition at approximately 500 K to a $L{1}_{2}$-type (Fe,Co,Ni)${}_{3}\mathrm{Cr}$ structure. The calculated magnetic exchange interactions were dominantly of the antiferromagnetic type between Cr and any other alloy component and ferromagnetic between Fe, Co, and Ni. They yielded a Curie temperature (${T}_{\mathrm{C}}$) of 120 K, close to experimental findings. Despite the low value of ${T}_{\mathrm{C}}$, the global magnetic state strongly affects chemical and elastic interactions in this system. In particular, it significantly increases the ordering tendency in the ferromagnetic state compared to the paramagnetic one.