The body centered cubic (BCC) high entropy alloys MoNbTaW and MoNbTaVW show exceptional strength retention up to 1900K. The mechanistic origin of the retained strength is unknown yet is crucial for finding the best alloys across the immense space of BCC HEA compositions. Experiments on Nb-Mo, Fe-Si and Ti-Zr-Nb alloys report decreased mobility of edge dislocations, motivating a theory of strengthening of edge dislocations in BCC alloys. Unlike pure BCC metals and dilute alloys that are controlled by screw dislocation motion at low temperatures, the strength of BCC HEAs can be controlled by edge dislocations, and especially at high temperatures, due to the barriers created for edge glide through the random field of solutes. A parameter-free theory for edge motion in BCC alloys qualitatively and quantitatively captures the strength versus temperature for the MoNbTaW and MoNbTaVW alloys. A reduced analytic version of the theory then enables screening over >600,000 compositions in the Mo-Nb-Ta-V-W family, identifying promising new compositions with high retained strength and/or reduced mass density. Overall, the theory reveals an unexpected mechanism responsible for high temperature strength in BCC alloys and paves the way for theory-guided design of stronger high entropy alloys.
Plasticity in body centered cubic (bcc) refractory metals are largely due to the stress tensor induced either by solute or thermal activation. The mechanism of the solute atom(s) residence causes instability in such metals. Earlier research have considered the mechanism of oxygen (O) or carbon (C) in tungsten (W), even though the major component of the environment is nitrogen (N). In this article, the density functional theory (DFT) was employed to investigate the thermodynamic stable site for an interstitial solute (N or O) in the bcc refractory metals (Mo and Nb) by calculating the equilibri…
We report on the production and characterization of a high-entropy alloy in the refractory Zr-Nb-Ti-V-Hf system. Equiatomic ingots were produced by arc and levitation melting, and were subsequently homogenized by high-temperature annealing. We obtained a coarse-grained, single-phase high-entropy alloy, with a homogeneous distribution of the constituting elements. The phase is a chemically disordered solid solution, based on a bcc lattice with a lattice parameter of 0.336(5) nm.
Refractory high entropy alloys containing elements from the Ti, V and Cr columns of the periodic table form body centered cubic (BCC) structures. Elements from the Ti column are noteworthy because they take the BCC structure at high temperature but undergo a shear instability and transform to the hexagonal (HCP) structure at low temperature. We show that the instability of these elements impacts the properties of the HEAs that contain them. In particular, the shear moduli are greatly reduced, causing increased dynamic contributions to lattice distortion. Relatively large size differences betwe…
The interactions between solute atoms and crystalline defects such as vacancies, dislocations, and grain boundaries play an essential role in determining physical, chemical and mechanical properties of solid-solution alloys. Here we present a universal correlation between two electronic factors and the solute-defect interaction energies in binary alloys of body-centered-cubic (bcc) refractory metals (such as W and Ta) with transition-metal substitutional solutes. One electronic factor is the bimodality of the d-orbital local density of states for a matrix atom at the substitutional site, and t…
New approaches for the design of alloy systems with multiprincipal elements is recently researched in refractory materials field. However, most research aimed at arc melting process with weakness of coarsening of grains and inhomogeneous microstructure of segregation of elements during the cooling. This study aims to design and fabricate high-entropy alloy with powder metallurgy. In this study, a refractory high entropy alloys with composition near AlMo0.5NbTa0.5TiZr were produced by powder metallurgy. The alloy consists of two body-centered cubic (BCC) phases. One phase was disordered BCC enr…
Application of isotropic pressure or uniaxial strain alters the elastic properties of materials; sufficiently large strains can drive structural transformations. Linear elasticity describes stability against infinitesimal strains, while nonlinear elasticity describes the response to finite deformations. It was previously shown that uniaxial strain along [100] drives refractory metals and alloys towards mechanical instabilities. These include an extensional instability, and a symmetry-breaking orthorhombic distortion caused by a Jahn-Teller-Peierls instability that splays the cubic lattice vect…
Whereas exceptional mechanical and radiation performances have been found in the emergent medium- and high-entropy alloys (MEAs and HEAs), the importance of their complex atomic environment, reflecting diversity in atomic size and chemistry, to defect transport has been largely unexplored at the atomic level. Here we adopt a local structure approach based on the atomic pair distribution function measurements in combination with density functional theory calculations to investigate a series of body-centered cubic (BCC) MEAs and HEAs. Our results demonstrate that all alloys exhibit local lattice…
Developing ductile refractory BCC alloys has remained a challenge. The intrinsic ductility (D) of an alloy is the ratio of surface energy ($γ_s$) and unstable stacking fault energy ($γ_{usfe}$). Lowering the valence electron concentration has been shown to improve the intrinsic ductility of refractory alloys. However, Re has been widely used to ductilize W, contrary to the low valency criteria suggested in the literature. Here we use density functional theory to calculate the enthalpy of formation, $γ_{usfe}$ and $γ_s$ of Group IV, V, VI elements and their 25 equiatomic binary alloys in BCC cr…
Crystal forming ability of amorphous refractory metals under nanoindentation: a molecular dynamics study
Czech Technical University in Prague（布拉格捷克技术大学）；Catalan Institute of Nanoscience and Nanotechnology (ICN2)（加泰罗尼亚纳米科学和技术研究所）；University of Southampton（南安普顿大学）
Energy efficiency is motivating the search for new high-temperature metals. Some new body-centered-cubic random multicomponent "high entropy alloys (HEAs)" based on refractory elements (Cr-Mo-Nb-Ta-V-W-Hf-Ti-Zr) possess exceptional strengths at high temperatures but the physical origins of this outstanding behavior are not known. Here we show, using integrated neutron-diffraction (ND), high-resolution transmission electron microscopy (HRTEM), and theory, that the high strength and strength retention of a NbTaVTi alloy and a new high-strength/low-density CrMoNbV alloy are attributable to edge d…
Effect of cold rolling strain on the microstructural evolution in equimolar MoNbTaTiZr refractory complex concentrated alloy: Comprehensive characterization
Atomistic and data-driven insights into the local slip resistances in random refractory multi-principal element alloys
South China University of Technology（华南理工大学）；University of Oklahoma（俄克拉荷马大学）；Stanford University（斯坦福大学）；University of California, Santa Barbara（加利福尼亚大学圣塔芭芭拉分校）
Cracking the case: fluctuations enhance ductility in refractory alloys
École Polytechnique Fédérale de Lausanne (EPFL)（洛桑联邦理工学院）；Laboratory of materials design and simulation (MADES), Institute of Materials, École Polytechnique Fédérale de Lausanne (EPFL)（洛桑联邦理工学院材料研究所材料设计与模拟实验室）；National Centre for Computational Design and Discovery of Novel Materials (MARVEL), École Polytechnique Fédérale de Lausanne (EPFL)（洛桑联邦理工学院新型材料计算设计与发现国家中心）；EMPA - Swiss Federal Laboratories for Materials Science and Technology（瑞士联邦材料科学与技术研究院）；Laboratory for Multiscale Modeling in Mechanics (LAMMM), Institute of Mechanical Engineering, École Polytechnique Fédérale de Lausanne (EPFL)（洛桑联邦理工学院机械工程学院多尺度力学建模实验室）；School of Engineering, Brown University, Providence, RI 02906 USA（布朗大学工程学院）
Body-centered cubic (bcc) refractory multicomponent alloys are of great interest due to their remarkable strength at high temperatures. Meanwhile, further optimizing the chemical compositions of these alloys to achieve a combination of high strength and room-temperature ductility remains challenging, which would require systematic predictions of the correlated alloy properties across a vast compositional space. In the present work, we performed first-principles calculations with the special quasi-random structure (SQS) method to predict the unstable stacking fault energy ($γ_{usf}$) of the $(1…
The high entropy alloy containing refractory metals Mo-Nb-Ta-W has a body centered cubic structure, which is not surprising given the complete mutual solubility in BCC solid solutions of all pairs of the constituent elements. However, first principles total energy calculations for the binaries reveal a set of distinct energy minimizing structures implying the likelihood of chemically ordered low temperature phases. We apply a hybrid Monte Carlo and molecular dynamics method to evaluate the temperature-dependent chemical order. At 300K a cesium-chloride ordering emerges between mixed (Nb,Ta) si…
Developing a single-phase and nanograined refractory high-entropy alloy ZrHfNbTaW with ultrahigh hardness by phase transformation via high-pressure torsion
Lattice Parameter is an important material feature in High Entropy Alloy (HEA) Design. Vegards Law is typically used to estimate lattice parameters but is often inaccurate for metal alloys due to an inability to account for charge transfer which can affect atomic volumes. The present study used ab initio simulation to calculate bond lengths between atoms of dissimilar elements in B2 intermetallic compounds which was then combined with a bond counting model to produce a model to estimate the lattice parameters of Refractory BCC HEAS. The model was tested using a supercell method which modeled v…
The phase diagram of numerous materials of technological importance features high-symmetry high-temperature phases that exhibit phonon instabilities. Leading examples include shape-memory alloys, as well as ferroelectric, refractory, and structural materials. The thermodynamics of these phases have proven challenging to handle by atomistic computational thermodynamic techniques, due to the occurrence of constant anharmonicity-driven hopping between local low-symmetry distortions, while maintaining a high-symmetry time-averaged structure. To compute the free energy in such phases, we propose to…
The ability to predict the composition- and temperature-dependent stability of refractory complex concentrated alloys (RCCAs) is vital to the design of high-temperature structural alloys. Here, we present a model based on first-principles calculations to predict the thermodynamic stability of multicomponent equimolar solid solutions in a high-throughput manner and apply it to screen over 20,000 compositions. We develop a database that contains pairwise mixing enthalpy of 17 refractory metals using density-functional theory (DFT)-based total energy calculations. To these, we fit thermodynamic s…
A simple fitting approach is used for modeling the compressive yield strength of body centered cubic (bcc) solid solution high entropy alloys in Al-Hf-Nb-Mo-Ta-Ti-V-Zr system. It is proposed that the yield strength could be modeled by a polynomial where the experimental data can be used for finding the polynomial coefficients. The results show that the proposed polynomial could model the yield strength of solid solution alloys relatively well. The developed polynomial is used for predicting the strength of RHEAs in Hf-Mo-Nb-Ta-Ti-V-Zr system. It is observed that the yield strength of alloys wi…
Nanocrystalline alloys (nanoalloys) are prone to grain growth. It is known that grain boundary segregation and precipitation can stabilize nanoalloys, but the stabilization becomes less effective at high temperatures and adding grain growth inhibitors often reduces sinterability. Herein, we have simultaneously achieved improved sinterability and exceptional high-temperature stability for a class of MoNbTaTiW-based refractory high-entropy nanoalloys (RHENs). Bulk pellets of RHENs were fabricated through planetary ball milling and spark plasma sintering, achieving 93-96% relative densities with …
Refractory high entropy alloys (RHEA) have been proven to have excellent mechanical properties with a potential use as protective thin films. However, the combination of high hardness with low friction and wear is a major challenge in the design of self lubricating RHEA films. In this study, we show that designing of NbMoWTa/Ag multilayered films give a remarkable reduction in friction and at same time maintain high hardness. Interestingly, it's found that the bcc superlattice dominates in both layers and the interfaces are highly coherent when the individual layer thickness h is reduced below…
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 on 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…
Electronic manifolds for extrapolative alloy discovery
School of Computational Science and Engineering, Georgia Institute of Technology（计算科学与工程学学院，佐治亚理工学院）；School of Chemical and Biomolecular Engineering, Georgia Institute of Technology（化学与生物分子工程学学院，佐治亚理工学院）；School of Civil and Environmental Engineering, Georgia Institute of Technology（土木与环境工程学学院，佐治亚理工学院）
Emergent B2 chemical orderings in the AlTiVNb and AlTiCrMo refractory high-entropy superalloys studied via first-principles theory and atomistic modelling
结合从头算电子结构理论与原子尺度蒙特卡罗模拟，研究了 AlTiVNb 和 AlTiCrMo 难熔高熵高温合金的相稳定性，揭示了高温下由 Al 和 Ti 驱动的 B2 化学有序及其对电子结构和电阻率的影响。
Cu-refractory metal composites containing Cr, Mo or W were subjected to severe plastic deformation using room temperature high-pressure torsion (HPT). A lamellar microstructure developed in each of the composites at equivalent strains of ~75. The refractory metals developed {hkl}<111> fibre textures with a slight tilt to the tangential direction. This texture was stronger and more clearly defined in Mo and W than in Cr. By applying additional HPT deformation to these samples, perpendicular to the original shear strain, it was found that the lamellar structure of Cu30Mo70 and Cu20W80 (wt.%) com…
Thermal and electrical conductivity of a refractory high-entropy alloy after high-pressure torsion: Electron versus phonon contributions
WPI, International Institute for Carbon Neutral Energy Research (WPI-I2CNER), Kyushu University（九州大学碳中和社会能源研究国际中心）；School of Mechanical Engineering, FEM, University of Campinas, UNICAMP（坎皮纳斯大学机械工程学院）；School of Applied Sciences, University of Campinas, FCA-UNICAMP（坎皮纳斯大学应用科学学院）；Department of Materials, Faculty of Engineering, Kyushu University（九州大学工学分部材料系）
Refractory multi-element alloys (RMEA) with body-centered cubic (bcc) structure have been the object of much research over the last decade due to their high potential as candidate materials for high-temperature applications. Most of these alloys display a remarkable strength at high temperatures, which cannot be explained by the standard model of bcc plasticity dominated by thermally-activated screw dislocation motion. Recent research on Nb-Mo-Ta-W alloys points to a heightened role of edge dislocations on deformation, which is generally attributed to atomic-level chemical fluctuations in the …
Phase selection in Ti-Zr-Hf-Al high-entropy alloys was investigated by in-situ high-energy X$-$ray diffraction, single-crystal X$-$ray diffraction, and density-functional theory based electronic-structure methods that address disorder and vacancies, predicting formation enthalpy and chemical short-range order (SRO). Samples with varying Al content were synthesized, characterized, and computationally assessed to ascertain the composition-dependent phase selection, as increased Al content often acts as a stabilizer of a body-centered-cubic structure. Equiatomic TiZrHfAl was especially interestin…
Refractory high entropy alloys (R-HEAs) are having properties and uses as high strength and high hardness materials for ambient and high temperature, aerospace and nuclear radiation tolerance applications, orthopedic applications etc. The mechanical properties like yield strength and ductility of TaNbHfZr R-HEA depend on the local nanostructure and chemical ordering. In this study we have computationally obtained various properties of the TaNbHfZr alloy like the role of configurational entropy in the thermodynamic property, rate of evolution of nanostructure morphology in thermally annealed sy…
Equiatomic TaNbHfZr refractory high-entropy alloys (HEAs) were synthesized by arc-melting. The HEAs were annealed at 1800°C for different times, at maximum up to 8 days. Their on average body-centered cubic (bcc), solid-solution structure was confirmed by X-ray (XRD) and neutron (ND) diffraction, respectively. The HEAs are characterized by high average values of the static atomic displacements from the ideal lattice positions and the local internal strain. The short-range clustering (SRC) of a subset of atoms, enriched in Hf and Zr takes place perpendicular to the <1 0 0> directions. Furthermo…
Ductility and Brittle Fracture of Tungsten by Disconnection Pile-up on Twin Boundaries
Lawrence Livermore National Laboratory（劳伦斯利弗莫尔国家实验室）；Los Alamos National Laboratory（洛斯阿拉莫斯国家实验室）；University of California Irvine（加州大学尔湾分校）；University of California Los Angeles（加州大学洛杉矶分校）；Lehigh University（理海大学）；Northwestern University（西北大学）
Three novel precipitation strengthened bcc alloys which exhibit a smooth microstructural gradient with composition have been fabricated in bulk form by induction casting. All three alloys are comprised of a mixture of disordered A2-(Fe, Cr) and L2$_1$-ordered (Ni, Fe)$_{2}$AlTi type phases both as-cast and after long-term annealing at 900 $^{\circ}$C. The ratio of disordered to ordered phase, primary dendrite fraction, and overall microstructural coarseness all decrease as Cr is replaced by Al and Ti. Differences in phase composition are quantified through domain averaged principal component a…
We investigate the strain-rate-dependent mechanical behavior and deformation mechanisms of a refractory high entropy alloy, Ti29Zr24Nb23Hf24 (at.%), with a single-phase body-centered cubic (BCC) structure. High-temperature compression tests were conducted at temperatures from 700 to 1100°C at strain rates ranging from 10-3 to 10 s-1. A sudden stress drop after yield point was observed at higher temperatures and lower strain rates with the Zener-Holloman parameter, lnZ, in the range of 17.2-20.7. Such a softening behavior can be related to the interaction of dislocations with short-range cluste…
