Tuning element distribution, structure and properties by composition in high-entropy alloys.

High-entropy alloys are a class of materials that contain five or more elements in near-equiatomic proportions1,2. Their unconventional compositions and chemical structures hold promise for achieving unprecedented combinations of mechanical properties3-8. Rational design of such alloys hinges on an understanding of the composition-structure-property relationships in a near-infinite compositional space9,10. Here we use atomic-resolution chemical mapping to reveal the element distribution of the widely studied face-centred cubic CrMnFeCoNi Cantor alloy2 and of a new face-centred cubic alloy, CrFeCoNiPd. In the Cantor alloy, the distribution of the five constituent elements is relatively random and uniform. By contrast, in the CrFeCoNiPd alloy, in which the palladium atoms have a markedly different atomic size and electronegativity from the other elements, the homogeneity decreases considerably; all five elements tend to show greater aggregation, with a wavelength of incipient concentration waves11,12 as small as 1 to 3 nanometres. The resulting nanoscale alternating tensile and compressive strain fields lead to considerable resistance to dislocation glide. In situ transmission electron microscopy during straining experiments reveals massive dislocation cross-slip from the early stage of plastic deformation, resulting in strong dislocation interactions between multiple slip systems. These deformation mechanisms in the CrFeCoNiPd alloy, which differ markedly from those in the Cantor alloy and other face-centred cubic high-entropy alloys, are promoted by pronounced fluctuations in composition and an increase in stacking-fault energy, leading to higher yield strength without compromising strain hardening and tensile ductility. Mapping atomic-scale element distributions opens opportunities for understanding chemical structures and thus providing a basis for tuning composition and atomic configurations to obtain outstanding mechanical properties.

Extreme Fermi Surface Smearing in a Maximally Disordered Concentrated Solid Solution.

We show that the Fermi surface can survive the presence of extreme compositional disorder in the equiatomic alloy Ni_{0.25}Fe_{0.25}Co_{0.25}Cr_{0.25}. Our high-resolution Compton scattering experiments reveal a Fermi surface which is smeared across a significant fraction of the Brillouin zone (up to 40% of 2π/a). The extent of this smearing and its variation on and between different sheets of the Fermi surface have been determined, and estimates of the electron mean free path and residual resistivity have been made by connecting this smearing with the coherence length of the quasiparticle states.

Lattice Distortion and Phase Stability of Pd-Doped NiCoFeCr Solid-Solution Alloys.

In the present study, we have revealed that (NiCoFeCr)100-xPdx (x= 1, 3, 5, 20 atom%) high-entropy alloys (HEAs) have both local- and long-range lattice distortions by utilizing X-ray total scattering, X-ray diffraction, and extended X-ray absorption fine structure methods. The local lattice distortion determined by the lattice constant difference between the local and average structures was found to be proportional to the Pd content. A small amount of Pd-doping (1 atom%) yields long-range lattice distortion, which is demonstrated by a larger (200) lattice plane spacing than the expected value from an average structure, however, the degree of long-range lattice distortion is not sensitive to the Pd concentration. The structural stability of these distorted HEAs under high-pressure was also examined. The experimental results indicate that doping with a small amount of Pd significantly enhances the stability of the fcc phase by increasing the fcc-to-hcp transformation pressure from ~13.0 GPa in NiCoFeCr to 20-26 GPa in the Pd-doped HEAs and NiCoFeCrPd maintains its fcc lattice up to 74 GPa, the maximum pressure that the current experiments have reached.

Nanoprecipitates to Enhance Radiation Tolerance in High-Entropy Alloys.

The growth of advanced energy technologies for power generation is enabled by the design, development, and integration of structural materials that can withstand extreme environments, such as high temperatures, radiation damage, and corrosion. High-entropy alloys (HEAs) are a class of structural materials in which suitable chemical elements in four or more numbers are mixed to typically produce single-phase concentrated solid solution alloys (CSAs). Many of these alloys exhibit good radiation tolerance like limited void swelling and hardening up to relatively medium radiation doses (tens of displacements per atom (dpa)); however, at higher radiation damage levels (>50 dpa), some HEAs suffer from considerable void swelling limiting their near-term acceptance for advanced nuclear reactor concepts. In this study, we developed a HEA containing a high density of Cu-rich nanoprecipitates distributed in the HEA matrix. The Cu-added HEA, NiCoFeCrCu0.12, shows excellent void swelling resistance and negligible radiation-induced hardening upon irradiation up to high radiation doses (i.e., higher than 100 dpa). The void swelling resistance of the alloy is measured to be significantly better than NiCoFeCr CSA and austenitic stainless steels. Density functional theory simulations predict lower vacancy and interstitial formation energies at the coherent interfaces between Cu-rich nanoprecipitates and the HEA matrix. The alloy maintained a high sink strength achieved via nanoprecipitates and the coherent interface with the matrix at a high radiation dose (∼50 dpa). From our experiments and simulations, the effective recombination of radiation-produced vacancies and interstitials at the coherent interfaces of the nanoprecipitates is suggested to be the critical mechanism responsible for the radiation tolerance of the alloy. The materials design strategy based on incorporating a high density of interfaces can be applied to high-entropy alloy systems to improve their radiation tolerance.

The Effects of Alloying Elements Cr, Al, and Si on Oxidation Behaviors of Ni-Based Superalloys.

Oxidation behaviors of three Ni-based model alloys and pure Ni in the temperature range of 700-1200 °C are investigated to reveal effects of Cr, Al, and Si on the oxidation resistance of Ni-based superalloys. The formation and integrity of consecutive chromia or alumina layers are important for excellent oxidation resistance. The addition of 20 at.% Cr can effectively improve the oxidation resistance of Ni-based alloys by forming a thin chromia film below 1000 °C, while adding 15 at.% Al has a beneficial effect on the oxidation resistance of Ni-based alloys at temperatures above 900 °C. The addition of 2 at.% Si to Ni-Al alloy is insufficient to form a protective SiO2 layer but can accelerate the formation of alumina, which enables Ni-Al alloy to form a consecutive inner alumina layer at a relatively low temperature of 800 °C and further improve the oxidation resistance above 800 °C.

Interpreting nanovoids in atom probe tomography data for accurate local compositional measurements.

Quantifying chemical compositions around nanovoids is a fundamental task for research and development of various materials. Atom probe tomography (APT) and scanning transmission electron microscopy (STEM) are currently the most suitable tools because of their ability to probe materials at the nanoscale. Both techniques have limitations, particularly APT, because of insufficient understanding of void imaging. Here, we employ a correlative APT and STEM approach to investigate the APT imaging process and reveal that voids can lead to either an increase or a decrease in local atomic densities in the APT reconstruction. Simulated APT experiments demonstrate the local density variations near voids are controlled by the unique ring structures as voids open and the different evaporation fields of the surrounding atoms. We provide a general approach for quantifying chemical segregations near voids within an APT dataset, in which the composition can be directly determined with a higher accuracy than STEM-based techniques.

Effects of chemical alternation on damage accumulation in concentrated solid-solution alloys.

Single-phase concentrated solid-solution alloys (SP-CSAs) have recently gained unprecedented attention due to their promising properties. To understand effects of alloying elements on irradiation-induced defect production, recombination and evolution, an integrated study of ion irradiation, ion beam analysis and atomistic simulations are carried out on a unique set of model crystals with increasing chemical complexity, from pure Ni to Ni80Fe20, Ni50Fe50, and Ni80Cr20 binaries, and to a more complex Ni40Fe40Cr20 alloy. Both experimental and simulation results suggest that the binary and ternary alloys exhibit higher radiation resistance than elemental Ni. The modeling work predicts that Ni40Fe40Cr20 has the best radiation tolerance, with the number of surviving Frenkel pairs being factors of 2.0 and 1.4 lower than pure Ni and the 80:20 binary alloys, respectively. While the reduced defect mobility in SP-CSAs is identified as a general mechanism leading to slower growth of large defect clusters, the effect of specific alloying elements on suppression of damage accumulation is clearly demonstrated. This work suggests that concentrated solid-solution provides an effective way to enhance radiation tolerance by creating elemental alternation at the atomic level. The demonstrated chemical effects on defect dynamics may inspire new design principles of radiation-tolerant structural alloys for advanced energy systems.

High pressure synthesis of a hexagonal close-packed phase of the high-entropy alloy CrMnFeCoNi.

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.

Instability Analysis and Free Volume Simulations of Shear Band Directions and Arrangements in Notched Metallic Glasses.

As a commonly used method to enhance the ductility in bulk metallic glasses (BMGs), the introduction of geometric constraints blocks and confines the propagation of the shear bands, reduces the degree of plastic strain on each shear band so that the catastrophic failure is prevented or delayed, and promotes the formation of multiple shear bands. The clustering of multiple shear bands near notches is often interpreted as the reason for improved ductility. Experimental works on the shear band arrangements in notched metallic glasses have been extensively carried out, but a systematic theoretical study is lacking. Using instability theory that predicts the onset of strain localization and the free-volume-based finite element simulations that predict the evolution of shear bands, this work reveals various categories of shear band arrangements in double edge notched BMGs with respect to the mode mixity of the applied stress fields. A mechanistic explanation is thus provided to a number of related experiments and especially the correlation between various types of shear bands and the stress state.

Exceptional damage-tolerance of a medium-entropy alloy CrCoNi at cryogenic temperatures.

High-entropy alloys are an intriguing new class of metallic materials that derive their properties from being multi-element systems that can crystallize as a single phase, despite containing high concentrations of five or more elements with different crystal structures. Here we examine an equiatomic medium-entropy alloy containing only three elements, CrCoNi, as a single-phase face-centred cubic solid solution, which displays strength-toughness properties that exceed those of all high-entropy alloys and most multi-phase alloys. At room temperature, the alloy shows tensile strengths of almost 1 GPa, failure strains of ∼70% and KJIc fracture-toughness values above 200 MPa m(1/2); at cryogenic temperatures strength, ductility and toughness of the CrCoNi alloy improve to strength levels above 1.3 GPa, failure strains up to 90% and KJIc values of 275 MPa m(1/2). Such properties appear to result from continuous steady strain hardening, which acts to suppress plastic instability, resulting from pronounced dislocation activity and deformation-induced nano-twinning.

Direct Observation of Defect Range and Evolution in Ion-Irradiated Single Crystalline Ni and Ni Binary Alloys.

Energetic ions have been widely used to evaluate the irradiation tolerance of structural materials for nuclear power applications and to modify material properties. It is important to understand the defect production, annihilation and migration mechanisms during and after collision cascades. In this study, single crystalline pure nickel metal and single-phase concentrated solid solution alloys of 50%Ni50%Co (NiCo) and 50%Ni50%Fe (NiFe) without apparent preexisting defect sinks were employed to study defect dynamics under ion irradiation. Both cross-sectional transmission electron microscopy characterization (TEM) and Rutherford backscattering spectrometry channeling (RBS-C) spectra show that the range of radiation-induced defect clusters far exceed the theoretically predicted depth in all materials after high-dose irradiation. Defects in nickel migrate faster than in NiCo and NiFe. Both vacancy-type stacking fault tetrahedra (SFT) and interstitial loops coexist in the same region, which is consistent with molecular dynamics simulations. Kinetic activation relaxation technique (k-ART) simulations for nickel showed that small vacancy clusters, such as di-vacancies and tri-vacancies, created by collision cascades are highly mobile, even at room temperature. The slower migration of defects in the alloy along with more localized energy dissipation of the displacement cascade may lead to enhanced radiation tolerance.

Quantum Critical Behavior in a Concentrated Ternary Solid Solution.

The face centered cubic (fcc) alloy NiCoCrx with x ≈ 1 is found to be close to the Cr concentration where the ferromagnetic transition temperature, Tc, goes to 0. Near this composition these alloys exhibit a resistivity linear in temperature to 2 K, a linear magnetoresistance, an excess -TlnT (or power law) contribution to the low temperature heat capacity, and excess low temperature entropy. All of the low temperature electrical, magnetic and thermodynamic properties of the alloys with compositions near x ≈ 1 are not typical of a Fermi liquid and suggest strong magnetic fluctuations associated with a quantum critical region. The limit of extreme chemical disorder in this simple fcc material thus provides a novel and unique platform to study quantum critical behavior in a highly tunable system.

Enhancing radiation tolerance by controlling defect mobility and migration pathways in multicomponent single-phase alloys.

A grand challenge in material science is to understand the correlation between intrinsic properties and defect dynamics. Radiation tolerant materials are in great demand for safe operation and advancement of nuclear and aerospace systems. Unlike traditional approaches that rely on microstructural and nanoscale features to mitigate radiation damage, this study demonstrates enhancement of radiation tolerance with the suppression of void formation by two orders magnitude at elevated temperatures in equiatomic single-phase concentrated solid solution alloys, and more importantly, reveals its controlling mechanism through a detailed analysis of the depth distribution of defect clusters and an atomistic computer simulation. The enhanced swelling resistance is attributed to the tailored interstitial defect cluster motion in the alloys from a long-range one-dimensional mode to a short-range three-dimensional mode, which leads to enhanced point defect recombination. The results suggest design criteria for next generation radiation tolerant structural alloys.

On the correlation between microscopic structural heterogeneity and embrittlement behavior in metallic glasses.

In order to establish a relationship between microstructure and mechanical properties, we systematically annealed a Zr-based bulk metallic glass (BMG) at 100 ~ 300 °C and measured their mechanical and thermal properties. The as-cast BMG exhibits some ductility, while the increase of annealing temperature and time leads to the transition to a brittle behavior that can reach nearly-zero fracture energy. The differential scanning calorimetry did not find any significant changes in crystallization temperature and enthalpy, indicating that the materials still remained fully amorphous. Elastic constants measured by ultrasonic technique vary only slightly with respect to annealing temperature and time, which does obey the empirical relationship between Poisson's ratio and fracture behavior. Nanoindentation pop-in tests were conducted, from which the pop-in strength mapping provides a "mechanical probe" of the microscopic structural heterogeneities in these metallic glasses. Based on stochastically statistic defect model, we found that the defect density decreases with increasing annealing temperature and annealing time and is exponentially related to the fracture energy. A ductile-versus-brittle behavior (DBB) model based on the structural heterogeneity is developed to identify the physical origins of the embrittlement behavior through the interactions between these defects and crack tip.

Influence of chemical disorder on energy dissipation and defect evolution in concentrated solid solution alloys.

A grand challenge in materials research is to understand complex electronic correlation and non-equilibrium atomic interactions, and how such intrinsic properties and dynamic processes affect energy transfer and defect evolution in irradiated materials. Here we report that chemical disorder, with an increasing number of principal elements and/or altered concentrations of specific elements, in single-phase concentrated solid solution alloys can lead to substantial reduction in electron mean free path and orders of magnitude decrease in electrical and thermal conductivity. The subsequently slow energy dissipation affects defect dynamics at the early stages, and consequentially may result in less deleterious defects. Suppressed damage accumulation with increasing chemical disorder from pure nickel to binary and to more complex quaternary solid solutions is observed. Understanding and controlling energy dissipation and defect dynamics by altering alloy complexity may pave the way for new design principles of radiation-tolerant structural alloys for energy applications.