Additive Manufacturing-Refractory HEAs for Extreme Environments: Oxidation Kinetics, Scale Evolution, and Protection

QI Hongqiang; YAN Ming

doi:10.3969/j.issn.1674-6457.2025.12.002

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Journal of Netshape Forming Engineering ›› 2025, Vol. 17 ›› Issue (12) : 15-24. DOI: 10.3969/j.issn.1674-6457.2025.12.002

Advanced Forming Engineering of High-Entropy and Amorphous Alloys

Additive Manufacturing-Refractory HEAs for Extreme Environments: Oxidation Kinetics, Scale Evolution, and Protection

QI Hongqiang, YAN Ming^*

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Abstract

Refractory high-entropy alloys (RHEAs) are regarded as promising next-generation structural materials for ultrahigh-temperature applications due to their excellent mechanical properties at high temperatures. However, their practical deployment is hindered by their intrinsic susceptibility to oxidation. Additive manufacturing (AM), as an emerging fabrication technology, enables near-net-shape production of complex components and introduces unique solidification features that significantly affect the high-temperature oxidation behavior, thus becoming a major research focus. This review summarizes recent progress on the oxidation of additive manufacturing-refractory high-entropy alloys (AM-RHEAs). It begins by briefly outlining the principles of alloy design, representative AM processes, and the fundamental theories of metal oxidation. The coupled effects of AM on oxidation are then discussed: rapid solidification produces fine and hierarchical microstructures that promote the diffusion of protective elements and the formation of dense oxide scales, while processing-induced defects such as pores, cracks, and residual stresses accelerate oxygen ingress and trigger scale spallation. A comparison of different alloy systems indicates that Al-containing alloys can form a stable α-Al₂O₃ scale, whereas alloys containing Cr or Si achieve synergistic protection through the formation of Cr₂O₃, SiO₂, or complex oxides. Furthermore, this paper systematically reviews strategies for enhancing the oxidation resistance of AM-RHEAs, including post-processing techniques like hot isostatic pressing and annealing, as well as surface engineering methods such as aluminizing, siliconizing, and high-entropy silicide coatings. However, current challenges remain, such as an unclear understanding of long-term service mechanisms and an inadequate correlation between process parameters and performance. Future work should further integrate multi-scale computational simulations with in-situ characterization techniques to deepen the understanding of the oxidation behavior in complex environments, thereby promoting the engineering application of AM-RHEAs in extreme environments.

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refractory high-entropy alloys / additive manufacturing / high-temperature oxidation / thermal barrier coatings / microstructure

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QI Hongqiang, YAN Ming. Additive Manufacturing-Refractory HEAs for Extreme Environments: Oxidation Kinetics, Scale Evolution, and Protection[J]. Journal of Netshape Forming Engineering. 2025, 17(12): 15-24 https://doi.org/10.3969/j.issn.1674-6457.2025.12.002

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