Nanostructured High-Entropy Alloys with Multiple Principal Elements: Novel Alloy Design Concepts and Outcomes
TL;DR: A new approach for the design of alloys is presented in this paper, where high-entropy alloys with multi-principal elements were synthesized using well-developed processing technologies.
Abstract: 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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TL;DR: High entropy alloys (HEAs) are barely 12 years old as discussed by the authors, and the field has stimulated new ideas and inspired the exploration of the vast composition space offered by multi-principal element alloys.
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, as well as some established functional materials. Mechanical properties of 3d transition metal CCAs are equivalent to commercial austenitic stainless steels and nickel alloys, while some refractory metal CCAs show potential to extend the service strength and/or temperature of nickel superalloys. Detailed analyses of microstructures and properties allow two major HEA hypotheses to be resolved. Although the ‘entropy effect’ is not supported by the present data, it has nevertheless made an enduring contribution by inspiring a clearer understanding of the importance of configurational entropy on phase stability. The ‘sluggish diffusion’ hypothesis is also not supported by available data, but it motivates re-evaluation of a classical concept of metallic diffusion. Building on recent published work, the CCA field has expanded to include materials with metallic, ionic or covalent bonding. It also includes microstructures with any number of phases and any type of phases. Finally, the MPEA field is shown to include both structural and functional materials applications. A significant number of future efforts are recommended, with an emphasis on developing high-throughput experiments and computations for structural materials. The review concludes with a brief description of major accomplishments of the field and insights gained from the first 12 years of research. The field has lost none of its potency and continues to pose new questions and offer new possibilities. The vast range of complex compositions and microstructures remains the most compelling motivation for future studies.
4,693 citations
Cites background from "Nanostructured High-Entropy Alloys ..."
...One of the earliest papers defines HEAs as, “those composed of five or more principal elements in equimolar ratios” [6]....
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...Diffusion is proposed to be sluggish in HEAs [6,21]....
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...Given that commonly studied HEAs have extended SS phase fields (Section 4.4.1.4) and that IM phases often have restricted composition ranges, single-phase IM alloys are expected to be relatively uncommon (Section 2.3.1)....
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...Several thermodynamic models have been used to estimate the phases in HEAs....
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...Some papers introduce HEAs as equimolar alloys only and some use different values of SSS,ideal to specify HEAs....
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TL;DR: The concept of high entropy introduces a new path of developing advanced materials with unique properties, which cannot be achieved by the conventional micro-alloying approach based on only one dominant element as mentioned in this paper.
Abstract: This paper reviews the recent research and development of high-entropy alloys (HEAs) HEAs are loosely defined as solid solution alloys that contain more than five principal elements in equal or near equal atomic percent (at%) The concept of high entropy introduces a new path of developing advanced materials with unique properties, which cannot be achieved by the conventional micro-alloying approach based on only one dominant element Up to date, many HEAs with promising properties have been reported, eg, high wear-resistant HEAs, Co15CrFeNi15Ti and Al02Co15CrFeNi15Ti alloys; high-strength body-centered-cubic (BCC) AlCoCrFeNi HEAs at room temperature, and NbMoTaV HEA at elevated temperatures Furthermore, the general corrosion resistance of the Cu05NiAlCoCrFeSi HEA is much better than that of the conventional 304-stainless steel This paper first reviews HEA formation in relation to thermodynamics, kinetics, and processing Physical, magnetic, chemical, and mechanical properties are then discussed Great details are provided on the plastic deformation, fracture, and magnetization from the perspectives of crackling noise and Barkhausen noise measurements, and the analysis of serrations on stress–strain curves at specific strain rates or testing temperatures, as well as the serrations of the magnetization hysteresis loops The comparison between conventional and high-entropy bulk metallic glasses is analyzed from the viewpoints of eutectic composition, dense atomic packing, and entropy of mixing Glass forming ability and plastic properties of high-entropy bulk metallic glasses are also discussed Modeling techniques applicable to HEAs are introduced and discussed, such as ab initio molecular dynamics simulations and CALPHAD modeling Finally, future developments and potential new research directions for HEAs are proposed
4,394 citations
TL;DR: This work examined a five-element high-entropy alloy, CrMnFeCoNi, which forms a single-phase face-centered cubic solid solution, and found it to have exceptional damage tolerance with tensile strengths above 1 GPa and fracture toughness values exceeding 200 MPa·m1/2.
Abstract: High-entropy alloys are equiatomic, multi-element systems that can crystallize as a single phase, despite containing multiple elements with different crystal structures. A rationale for this is that the configurational entropy contribution to the total free energy in alloys with five or more major elements may stabilize the solid-solution state relative to multiphase microstructures. We examined a five-element high-entropy alloy, CrMnFeCoNi, which forms a single-phase face-centered cubic solid solution, and found it to have exceptional damage tolerance with tensile strengths above 1 GPa and fracture toughness values exceeding 200 MPa·m(1/2). Furthermore, its mechanical properties actually improve at cryogenic temperatures; we attribute this to a transition from planar-slip dislocation activity at room temperature to deformation by mechanical nanotwinning with decreasing temperature, which results in continuous steady strain hardening.
3,704 citations
TL;DR: In this metastability-engineering strategy, a transformation-induced plasticity-assisted, dual-phase high-entropy alloy (TRIP-DP-HEA) is designed, which combines the best of two worlds: extensive hardening due to the decreased phase stability known from advanced steels and massive solid-solution strengthening of high-ENTropy alloys.
Abstract: Metals have been mankind's most essential materials for thousands of years; however, their use is affected by ecological and economical concerns Alloys with higher strength and ductility could alleviate some of these concerns by reducing weight and improving energy efficiency However, most metallurgical mechanisms for increasing strength lead to ductility loss, an effect referred to as the strength-ductility trade-off Here we present a metastability-engineering strategy in which we design nanostructured, bulk high-entropy alloys with multiple compositionally equivalent high-entropy phases High-entropy alloys were originally proposed to benefit from phase stabilization through entropy maximization Yet here, motivated by recent work that relaxes the strict restrictions on high-entropy alloy compositions by demonstrating the weakness of this connection, the concept is overturned We decrease phase stability to achieve two key benefits: interface hardening due to a dual-phase microstructure (resulting from reduced thermal stability of the high-temperature phase); and transformation-induced hardening (resulting from the reduced mechanical stability of the room-temperature phase) This combines the best of two worlds: extensive hardening due to the decreased phase stability known from advanced steels and massive solid-solution strengthening of high-entropy alloys In our transformation-induced plasticity-assisted, dual-phase high-entropy alloy (TRIP-DP-HEA), these two contributions lead respectively to enhanced trans-grain and inter-grain slip resistance, and hence, increased strength Moreover, the increased strain hardening capacity that is enabled by dislocation hardening of the stable phase and transformation-induced hardening of the metastable phase produces increased ductility This combined increase in strength and ductility distinguishes the TRIP-DP-HEA alloy from other recently developed structural materials This metastability-engineering strategy should thus usefully guide design in the near-infinite compositional space of high-entropy alloys
2,403 citations
TL;DR: In this article, an equiatomic CoCrFeMnNi high-entropy alloy, which crystallizes in the face-centered cubic (fcc) crystal structure, was produced by arc melting and drop casting.
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.
2,181 citations