Key Takeaways & Executive Findings
- •• Addition of Y2O3 or CeO2 to AlCrFeNiCu high-entropy alloy coating refined the grain structure and modified solidification kinetics, significantly enhancing overall performance. • Doped coatings achieved hardness of 8.61 GPa (Y2O3) and 8.72 GPa (CeO2), with wear rate reductions of 41.3% and 38.0% respectively compared to the undoped coating. • Both modified coatings showed an order-of-magnitude decrease in self-corrosion current density in 0.1 mol/L KOH solution, indicating superior corrosion resistance. • Oxide-doped coatings maintained structural integrity after 90 min at 1200°C, while the undoped coating developed microcracks after only 30 min, demonstrating markedly improved high-temperature oxidation resistance.
Abstract
Y2O3 and CeO2 nanoparticles were individually incorporated into an AlCrFeNiCu coating applied to the surface of a Zr-4 rod. The microstructure, hardness, high-temperature fretting wear behavior, corrosion resistance, and high-temperature oxidation resistance of the coatings were comprehensively evaluated. The results demonstrate that the addition of Y2O3 or CeO2 notably modified the solidification kinetics of the molten pool, affected elemental diffusion pathways, and effectively refined the grain structure, thus significantly improving the overall performance of the AlCrFeNiCu coating. Specifically, the hardness of the AlCrFeNiCu coatings doped with Y2O3 and CeO2 reached 8.61 and 8.72 GPa, respectively, with corresponding wear rate reductions of 41.3% and 38.0% compared to the undoped coating. In a 0.1 mol/L KOH solution, the self-corrosion current densities of both modified coatings decreased by one order of magnitude in comparison to the unmodified AlCrFeNiCu coating. The oxidation behavior of both coatings conformed to parabolic kinetics, and the coatings retained their structural integrity after being exposed to air at 1200°C for 90 min, whereas the undoped coating exhibited microcracks after 30 min of exposure.
1. Introduction
Nuclear fuel cladding tubes, which encapsulate fuel pellets, serve as a critical safety barrier in reactors. Applying surface coatings to Zr alloy cladding presents a promising approach for enhancing accident tolerance, as it improves resistance to high-temperature steam oxidation while maintaining compatibility with existing reactor systems. Since 2017, high-entropy alloys (HEAs) such as V35Ti35Fe15Cr10Zr5 have been designed for nuclear applications [1]. Subsequent radiation resistance studies, initiated around 2019, have explored compositions like Ti2ZrHfV0.5Mo0.2 [2]. To date, refractory HEAs (RHEAs), including HfNbZrTi, Ti2ZrHfV0.5Mo0.2, TixWTaVCr, HfNbTaTiZr, and Mo0.5NbTiVCr0.25 as well as Mo0.5NbTiV0.5Zr0.25 [2–8], have demonstrated exceptional radiation tolerance, indicating strong potential for extreme nuclear environments. Based on the outstanding radiation resistance of HEAs, HEA coatings tailored for Zr alloys has been developed and fabricated via high-speed laser cladding (HSLC) [9–11].
HSLC is an advanced additive manufacturing technique that overcomes limitations of conventional cladding, such as excessive heat input and high dilution, by optimizing energy distribution during deposition. It enables higher processing speeds, improved efficiency, and reduced dilution [12–13]. The process involves rapid thermal cycles that modify grain growth, increase dislocation density, and enhance hardness and wear resistance. However, cracking remains a concern, necessitating careful evaluation of crack susceptibility. Studies indicate that incorporating minor amounts of rare earth oxides (e.g., CeO2, Y2O3, La2O3) refines grains, mitigates defects, and reduces cracking, thereby improving coating performance [14–16]. Among these, Y2O3 and CeO2 are widely utilized for enhancing strength and thermal stability. Their integration into HEA coatings—such as WMoTaNb, CoCrFeNiTiNb, FeCoNiCrMo, AlCoCrFeNiTi, AlCoCrFeNiCu, and FeCrNiMnAl—has proven effective in refining microstructure and boosting mechanical and corrosion resistance [17–21]. For example, the incorporation of Y2O3 led to a 26.5% increase in the microhardness of WMoTaNb, a 26.9% enhancement in the wear resistance of CoCrFeNiTiNb, and respective reductions of 60.3% and 40.3% in the oxidation rate and hot corrosion rate [17–18]. The addition of CeO2 reduced the crack sensitivity of the FeCoNiCrMo coating, increased its microhardness by 11.76%, and improved its corrosion resistance in a 3.5% NaCl solution [19]. The wear resistance of AlCoCrFeNiTi under dry-grinding and wet-grinding conditions increased by 55.14% and 50.69%, respectively [20].
In this study, AlCrFeNiCu coatings modified with Y2O3 and CeO2 were successfully deposited on Zr-4 substrates via HSLC. The influence of Y2O3 and CeO2 on microstructure, hardness, high-temperature fretting wear behavior, and corrosion resistance was systematically investigated, providing valuable insights for the development of rare earth oxide-reinforced HEA surface layers.
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Xiaona Ren, Zhipei Chen, Qingzhi Yan, Peng Wang, Wenchang Wang, Yao Wang, Changchun Ge, Yong Zhang (2025). Influence of Y2O3/CeO2 on the microstructure and properties of AlCrFeNiCu high-entropy alloy coating. Journal of Mineral Metallurgy and Materials Science. https://doi.org/10.1007/s12613-026-3413-x
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Frequently Asked Questions
What is the effect of Y2O3 and CeO2 on the AlCrFeNiCu high-entropy alloy coating?
The addition of Y2O3 or CeO2 nanoparticles modifies the solidification kinetics, refines the grain structure, and enhances the mechanical properties, corrosion resistance, and high-temperature oxidation resistance of the AlCrFeNiCu coating.
How did the rare earth oxides affect hardness and wear resistance?
The hardness of the AlCrFeNiCu coatings doped with Y2O3 and CeO2 reached 8.61 GPa and 8.72 GPa, respectively, with corresponding wear rate reductions of 41.3% and 38.0% compared to the undoped coating.
What was the improvement in corrosion resistance?
In a 0.1 mol/L KOH solution, the self-corrosion current densities of both modified coatings decreased by one order of magnitude compared to the unmodified AlCrFeNiCu coating, indicating significantly improved corrosion resistance.
How did the coatings behave under high-temperature oxidation?
The oxidation behavior of both doped coatings conformed to parabolic kinetics, and they retained structural integrity after exposure to air at 1200°C for 90 min. In contrast, the undoped coating exhibited microcracks after 30 min of exposure.
What fabrication technique was used for the coatings?
The coatings were fabricated via high-speed laser cladding (HSLC), an advanced additive manufacturing technique that optimizes energy distribution and enables higher processing speeds with reduced dilution.
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