Abstract

It has been 14 years since the discovery of the high-entropy alloys (HEAs), an idea of alloying which has reinvigorated materials scientists to explore unconventional alloy compositions and multicomponent alloy systems. Many authors have referred to these alloys as multi-principal element alloys (MPEAs) or complex concentrated alloys (CCAs) in order to place less restrictions on what constitutes an HEA. Regardless of classification, the research is rooted in the exploration of structure-properties and processing relations in these multicomponent alloys with the aim to surpass the physical properties of conventional materials. More recent studies show that some of these alloys undergo liquid phase separation, a phenomenon largely dictated by low entropy of mixing and positive mixing enthalpy. Studies posit that positive mixing enthalpy of the binary and ternary components contribute substantially to the formation of liquid miscibility gaps. The objective of this review is to bring forth and summarize the findings of the experiments which detail liquid phase separation (LPS) in HEAs, MPEAs, and CCAs and to draw parallels between HEAs and the conventional alloy systems which undergo liquid-liquid separation. Positive mixing enthalpy if not compensated by the entropy of mixing will lead to liquid phase separation. It appears that Co, Ni, and Ti promote miscibility in HEAs/CCAs/MPEAs while Cr, V, and Nb will raise the miscibility gap temperature and increase LPS. Moreover, addition of appropriate amounts of Ni to CoCrCu eliminates immiscibility, such as in cases of dendritically solidifying CoCrCuNi, CoCrCuFeNi, and CoCrCuMnNi.

Highlights

  • Many high-entropy alloys (HEAs)/concentrated alloys (CCAs)/multi-principal element alloys (MPEAs) solidify with a duplex microstructure, where the dendritic and interdendritic regions have large compositional and crystallographic differences [53,58,59,60,64]

  • Through the use of neutron transmission imaging techniques, the direct observation of liquid phase separation in metals was made possible via neutron radiographs taken during heating and cooling of immiscible CoCrCu alloys [72]

  • The first occurrence of liquid phase separation (LPS) in HEAs was observed by Hsu et al in 2007 with a study of the alloying behavior of AlCoCrCuNi-based HEAs with additions of Fe, Ag, and Au [106]

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Summary

Liquid Phase Separation

Liquid phase separation (LPS), a widely-observed phenomenon in metals, is related directly to the Gibbs free energy of the system, and the most prevailing cases are often two distinct immiscible liquids of varying compositions. There is often some degree of solubility between the alloying elements in a metallic system exhibiting LPS, each liquid will have its own equilibrium vapor pressure, such that the vapor pressures of both phases are the same, with a positive deviation from Raoult’s law. An alloy exhibiting liquid phase separation would not be suited for use as a structural material due to the heterogeneity of the microstructure; it may have potential use as a self-lubricating bearing material, such as the case with Cu-Pb. There have been several comprehensive reviews of Entropy 2018, 20, 890; doi:10.3390/e20110890 www.mdpi.com/journal/entropy. The scope of this review will focus on the liquid phase separation in the high-entropy alloy (HEA), complex concentrated alloy (CCA), and multi-principal element alloy (MPEA) systems

Thermodynamics of Liquid Phase Separation
Metastable Liquid Phase Separation
High-Entropy Alloys
Dendritic Microstructure
Microstructures Resulting from Liquid Phase Separation
HEAs Containing Cu
CoCrCuFeNi
Closing
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