Eutectic high-entropy alloys (EHEAs), combining the advantages of both eutectic alloys and high-entropy alloys (HEAs), possess good castability and superior comprehensive mechanical properties which are regarded as a revolutionary material system. In this paper, a current study of EHEAs is captured comprehensively for the first time, including basic theory, microstructure and deformation behavior, and alloy design. An in-depth analysis of the formation of different microstructures of EHEAs and their mechanical properties is presented, and four methods of designing EHEAs are summarized. Due to their unique characteristics, EHEAs show great potential in materials processing engineering. Here we give a comprehensive summary of their applications in welding, surface engineering, and additive manufacturing for the first time. Among them, EHEAs in welding are divided into three sections based on different welding techniques: fusion-based welding, solid-state welding, and diffusion reaction-based welding; EHEAs in surface engineering are separated into two parts: surface modification of bulk EHEAs and EHEA coatings; EHEAs in additive manufacturing are elaborated in two parts: laser powder bed fusion (LPBF) and laser direct energy deposition (LDED). Finally, a summary is given and a future outlook is prospected. 

Eutectic high-entropy alloys and their applications in materials processing engineering: A Review

Multi-phase multi-scale composite eutectic alloys containing micrometer-scale dendrites and nano structures provide an opportunity for the development of ultrahigh strength materials. Eutectic high entropy alloys (EHEAs) facilitate the design of eutectic alloys with such structures in the as-cast state due to the hysteretic diffusion effect characteristic of high entropy alloys. Nevertheless, the prevailing design approach for eutectic high-entropy alloys predominantly emphasizes biphase eutectics, with limited attention directed towards methods for designing multiphase eutectic structures. In this work, we propose a pseudo-ternary based idea to design and prepare multiphase multiscale FCC-based triple-phase eutectic high-entropy alloys, i.e., CoCrFeNi–NiAl-X. Using this strategy, a series of triple-phase EHEAs consisting of face-centered cubic (FCC), ordered body-centered cubic (B2), and Laves phase with topologically-close-packed structure (TCP) were successfully prepared by arc melting, like CoCrFeNi–NiAl–Nb. The four designed FCC-based multi-phase multi-scale EHEAs can be categorized into two main groups: 1) primary phase FCC and biphase or triple-phase eutectic; and 2) primary phase FCC, biphase eutectic and triple-phase eutectic. The designed FCC-based multi-phase multi-scale EHEAs exhibit promising mechanical properties. The design idea is not only applicable to the current work, but also provides a new strategy for the later design of other multi-phase multi-scale composite EHEAs, like CoCrFeNi–NiAl–Ta. 

Multi-phase FCC-based composite eutectic high entropy alloy with multi-scale microstructure

The strength and plasticity trade-off in metal materials can be effectively addressed by Eutectic High-Entropy Alloys (EHEAs) through the realization of heterogeneous biphase layered structures at both micrometer and nanometer scales. In this work, a series of (CoCrFeNi)88NbxW(12-x) EHEAs were prepared, and the effects of the synergistic of Nb and W elements on the microstructure and mechanical properties of CoCrFeNi High-Entropy Alloys (HEAs) were investigated. With the increase of Nb content and the decrease of W content, the microstructure of the alloy underwent three changes, from Face Center Cubic (FCC) + μ biphase to FCC + μ + Laves triple phase, and finally to FCC + Laves biphase. The strength of the alloy increases, but the compression rate decreases. Among these alloys, (CoCrFeNi)88Nb10W2 alloy exhibits exceptional mechanical properties. The synergistic effect of precipitation strengthening and grain boundary strengthening makes the yield strength, fracture strength, and plastic strain of the alloy are 1568 MPa, 2516 MPa, and 32 % respectively. In addition, in the CoCrFeNi HEAs, the weighted average atomic radius ratio (rm¯/rQ) is used to further precise the phase selection law of Laves phase and μ phase. When rm¯/rQ < 1.112, HEAs forms the μ phase, when 1.112 ≤ rm¯/rQ ≤ 1.14, HEAs forms the Laves + μ biphase, when rm¯/rQ > 1.14, HEAs forms the Laves phase. The results can provide a basis for synergistic strengthening and phase selection of CoCrFeNi HEAs. 

Synergistic effect of Nb and W alloying on the microstructure and mechanical properties of CoCrFeNi high entropy alloys

Eutectic high-entropy alloys (EHEAs) have combined both high-entropy alloys and eutectic alloy contributions, with excellent castability and high-temperature application potential. Yet, multielement/triple-phase eutectic high-entropy alloy (TEHEA) designs remain puzzling. This work proposed a new strategy based on an infinite solid solution and pseudo-ternary model to reveal the puzzle of TEHEAs. The designed triple-phase eutectic high-entropy alloys (TEHEAs) with more than seven elements were identified as face-centered cubic (FCC), ordered body-centered cubic (B2), and Laves phase structures. In this work, the alloy C showcases outstanding comprehensive mechanical properties, offering a novel avenue for the design of high-performance EHEAs.

A New Strategy for the Design of Triple-Phase Eutectic High-Entropy Alloys Based on Infinite Solid Solution and Pseudo-Ternary Method.

In this work, the properties of two high-entropy alloys (HEAs) Al25Cr20Fe20Ni35 and Al20Cr20Fe20Ni40 (at.%) were compared for potential application as bond coats in thermal barrier coatings (TBCs). For this reason, both their oxidation resistance under isothermal and thermal shock conditions, as well as diffusion phenomena occurring at the substrate-HEA diffusion couple interface, were investigated. It was determined that both alloys demonstrate good phase stability and oxidation resistance during prolonged exposure to air atmosphere at 1000°C. In the initial 100 h period, selective aluminum oxidation is responsible for the protective scale growth on both materials under both isothermal and thermal shock conditions. However, only the Al20Cr20Fe20Ni40 high entropy alloy maintains a single Al2O3 layer for over 1000 h of oxidation with cyclic temperature changes. On the other hand, diffusion studies indicate that mainly iron and chromium travel between the ferritic steel substrate and the HEAs. Aluminum diffusion is seemingly limited by the unexpected formation of a thin aluminum nitride layer at the interface between the materials. From all these results it can be concluded that the Al20Cr20Fe20Ni40 alloy shows more promise for application in TBCs based on high entropy materials than Al25Cr20Fe20Ni35. 

High-temperature oxidation and diffusion studies on selected Al–Cr–Fe–Ni high-entropy alloys for potential application in thermal barrier coatings

Microstructure and properties of a novel cost-effective FeNi-based eutectic high entropy alloys

A group of low-cost Fe40Ni(50-x)Cr10Mox high-entropy alloys (HEAs) without the Co element were proposed. The microstructure and properties were investigated. With the increase of Mo content, the microstructure changes from FCC single-phase to two-phase divorced eutectic, divorced eutectic + hypoeutectic, hypoeutectic, eutectic and hypereutectic, in which the two-phase is composed of FCC phase + σ phase. The yield strength of alloy increases with the increase of Mo content. Its strengthening mechanism transforms from solution strengthening to second phase strengthening and grain boundary strengthening. Mo-20 and Mo-22.5 have comprehensive mechanical properties, and their yield strength, fracture strength and plastic strain are 1103.1 MPa and 1127.9 MPa, 1924.5 MPa and 1881.7 MPa, 30.4% and 28.7% respectively. In addition, the revised equivalent Cr content (ECC) is proposed in the FeNiCrMo HEAs, ECC = at.%[Cr]+8/3 × at.%[Mo]. The eutectic composition can be precisely designed through the revised ECC and atomic content ratio (RI/F) of the intermetallic forming elements to the FCC forming elements in FeNiCrMo HEAs system. When 20 at.%≤Fe and Ni ≤ 40 at.%, and RI/F = ECC/[x × at.%Fe + y × at.%Ni] = 1.05 ± 0.3, FexNiyCrmMon is the eutectic high-entropy alloy. 

Precise design strategy of FeNiCrMo eutectic high-entropy alloys

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Microstructure and properties of a novel cost-effective FeNi-based eutectic high entropy alloys

Precise design strategy of FeNiCrMo eutectic high-entropy alloys