Metastable High-entropy Alloys Research Articles

Extremely high strength and work hardening ability in a metastable high entropy alloy

Design of multi-phase high entropy alloys uses metastability of phases to tune the strain accommodation by favoring transformation and/or twinning during deformation. Inspired by this, here we present Si containing dual phase Fe42Mn28Co10Cr15Si5 high entropy alloy (DP-5Si-HEA) exhibiting very high strength (1.15 GPa) and work hardening (WH) ability. The addition of Si in DP-5Si-HEA decreased the stability of f.c.c. (γ) matrix thereby promoting pronounced transformation induced plastic deformation in both as-cast and grain refined DP-5Si-HEAs. Higher yet sustained WH ability in fine grained DP-5Si-HEA is associated with the uniform strain partitioning among the metastable γ phase and resultant h.c.p. (ε) phase thereby resulting in total elongation of 12%. Hence, design of dual phase HEAs for improved strength and work hardenability can be attained by tuning the metastability of γ matrix through proper choice of alloy chemistry from the abundant compositional space of HEAs.

Twinning in metastable high-entropy alloys

Twinning is a fundamental mechanism behind the simultaneous increase of strength and ductility in medium- and high-entropy alloys, but its operation is not yet well understood, which limits their exploitation. Since many high-entropy alloys showing outstanding mechanical properties are actually thermodynamically unstable at ambient and cryogenic conditions, the observed twinning challenges the existing phenomenological and theoretical plasticity models. Here, we adopt a transparent approach based on effective energy barriers in combination with first-principle calculations to shed light on the origin of twinning in high-entropy alloys. We demonstrate that twinning can be the primary deformation mode in metastable face-centered cubic alloys with a fraction that surpasses the previously established upper limit. The present advance in plasticity of metals opens opportunities for tailoring the mechanical response in engineering materials by optimizing metastable twinning in high-entropy alloys.

Comparative study of hydrogen embrittlement in stable and metastable high-entropy alloys

We investigated the effects of hydrogen on the mechanical response and embrittlement behavior of Fe20Mn20Ni20Cr20Co and Fe30Mn10Cr10Co (at.%) alloys precharged with 100MPa hydrogen gas. These alloys can be classified as stable and metastable austenite-based high entropy alloys (HEAs), respectively. We carried out tensile tests at initial strain rates of 10−4 and 10−2s−1 at ambient temperature. Both HEAs revealed hydrogen embrittlement associated with localized plasticity-assisted intergranular crack initiation. It is important to note that hydrogen-assisted cracking of the metastable HEA occurred via localized plasticity for both the austenite and ε-martensite phases – an unusual observation for the latter.

Fatigue Crack Growth Behavior and Associated Microstructure in a Metastable High-Entropy Alloy

High-entropy alloys (HEAs) containing different kinds of high-concentration solute atoms provide new concepts for obtaining excellent balance of strength and ductility. In particular, a metastable dual-phase HEA (Fe30Mn10Cr10Co; FCC matrix and HCP second phase) shows superior ductility and strength owing to the transformation-induced plasticity effect associated with deformation-induced HCP-martensitic transformation. In this context, the fatigue properties of metastable HEAs are to be investigated towards practical applications as structure materials. In this study, the fatigue crack growth behaviors of HEA and type 316L austenitic stainless steel (FCC single phase) were comparatively examined. The crack growth rate of HEA was comparable to that of 316L. In HEA, the fatigue crack was covered by a large amount of HCP-martensite. In general, the HCP-martensite was cracked easily because of the smaller number of slip systems. However, the negative effect of HCP-martensite did not appear in the fatigue crack growth rate of HEA. By electron channeling contrast imaging, we found that the HCP-martensite beneath the fracture surface contained significant orientation gradient and high density of dislocations, indicating that HCP-martensite in the present Fe30Mn10Cr10Co HEA had high plastic deformability and associated stress accommodation capacity.

A new design concept for prevention of hydrogen-induced mechanical degradation: viewpoints of metastability and high entropy

‟How crack growth is prevented” is key to improve both fatigue and monotonic fracture resistances under an influence of hydrogen. Specifically, the key points for the crack growth resistance are hydrogen diffusivity and local ductility. For instance, type 304 austenitic steels show high hydrogen embrittlement susceptibility because of the high hydrogen diffusivity of bcc (α´) martensite. In contrast, metastability in specific austenitic steels enables fcc (γ) to hcp (ε) martensitic transformation, which decreases hydrogen diffusivity and increases strength simultaneously. As a result, even if hydrogen-assisted cracking occurs during monotonic tensile deformation, the ε-martensite acts to arrest micro-damage evolution when the amount of ε-martensite is limited. Thus, the formation of ε-martensite can decrease hydrogen embrittlement susceptibility in austenitic steels. However, a considerable amount of ε-martensite is required when we attempt to have drastic improvements of work hardening capability and strength level with respect to transformation-induced plasticity effect. Since the hcp structure contains a less number of slip systems than fcc and bcc, the less stress accommodation capacity often causes brittle-like failure when the ε-martensite fraction is large. Therefore, ductility of ε-martensite is another key when we maximize the positive effect of ε-martensitic transformation. In fact, ε-martensite in a high entropy alloy was recently found to be extraordinary ductile. Consequently, the metastable high entropy alloys showed low fatigue crack growth rates in a hydrogen atmosphere compared with conventional metastable austenitic steels with α´-martensitic transformation. We here present effects of metastability to ε-phase and configurational entropy on hydrogen-induced mechanical degradation including monotonic tension properties and fatigue crack growth resistance.

Localized Plasticity and Associated Cracking in Stable and Metastable High-Entropy Alloys Pre-Charged with Hydrogen

We investigated hydrogen embrittlement in Fe20Mn20Ni20Cr20Co and Fe30Mn10Cr10Co (at.%) alloys pre-charged with 100 MPa hydrogen gas by tensile testing at three initial strain rates of 10−4, 10−3, and 10−2 s−1 at ambient temperature. The alloys are classified as stable and metastable austenite-based high-entropy alloys (HEAs), respectively. Both HEAs showed the characteristic hydrogen-induced degradation of tensile ductility. Electron backscatter diffraction analysis indicated that the reduction in ductility by hydrogen pre-charging was associated with localized plasticity-assisted intergranular crack initiation. It should be noted as an important finding that hydrogen-assisted cracking of the metastable HEA occurred not through a brittle mechanism but through localized plastic deformation in both the austenite and ε-martensite phases.

Metastable high-entropy dual-phase alloys overcome the strength-ductility trade-off.

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.

Reactive spray processing of advanced materials: A.Lawley et al. (Drexel University, USA.)

We report the annealing time-dependent microstructures and deformation mechanisms of the novel face-centered cubic Fe49.5Mn30Co10Cr10C0.2Ti0.1V0.1Mo0.1 HEA. Three types of precipitates, σ-phase, Cr-rich MC-type carbides, and nano-scale (Ti, V, Mo)C, are present after cold-rolling and annealing at 600 °C. Such hierarchical precipitates could lead to sluggish recrystallization and grain growth upon annealing. The partially recrystallized microstructures and hierarchical precipitates could lead to a high yield strength even for prolonged annealing conditions. Deformation mechanisms change with annealing time. The materials annealed for short times (< 2 h) are deformed by dislocation glide, deformation twinning, and deformation-induced ε phase. A longer annealing time (> 10 h) triggers a multi-variant ε phase, reverse transformation from ε to γ, and the multi-step sequential transformation, γ → ε → reverse transformed γ from ε → ε transformed from the reverse transformed γ. Further, materials annealed for longer times shows a higher contribution of back stress strengthening, which could be attributed to the increase in γ/ε and γ/σ interfaces. The activation of various deformation mechanisms and high back stress strengthening could lead to a superior strain hardening capacity and strength-ductility combination (YS: 699 MPa, UTS: 1041 MPa, TE: 45%) of the material annealed for 10 h. The present work provides the novel microstructure design solution of the metastable high entropy alloys with exceptional mechanical properties, utilizing hierarchical precipitates, sequential deformation-induced phase transformation, and enhanced back stress strengthening.