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摘要: 以V?(4?5)Cr?(4?5)Ti合金為代表的釩合金具有高溫性能優異、抗輻照腫脹性能好、中子輻照活化性低等諸多優點，被視為先進核聚變反應堆最有潛力的候選包層結構材料之一。然而，釩合金在較高溫度下的氧化腐蝕及吸氧脆化問題仍是目前制約其實際應用和長壽命服役的重要因素。因此，提升釩合金的抗高溫氧化腐蝕性能，對于提高其服役溫度、延長其服役壽命以及拓寬其應用領域均具有重要意義。本文綜述了國內外有關提升釩合金抗高溫氧化腐蝕性能的三種主要方案，即添加抗氧化性元素、應用擴散型涂層和包覆型涂層，并對這些方案的主要特點、應用實例以及存在的問題進行了分析和討論。上述三種方案中，包覆型涂層由于可以將釩合金基體和服役環境完全隔離，因而具備更大的應用潛力。根據釩合金的應用特點，對先進包覆型抗氧化腐蝕涂層的發展趨勢和技術需求進行了展望，以期為釩合金抗高溫氧化腐蝕研究工作的深入開展提供借鑒。Abstract: Vanadium alloys are an attractive candidate material for advanced fusion reactors’ structural components. Some leading vanadium alloys, such as V?(4?5)Cr?(4?5)Ti alloy, exhibit several important advantages, including excellent strength at elevated temperatures, high resistance to neutron irradiation damage, inherently low long-term activation, as well as good fabricability and weldability. However, the corrosion and embrittlement via oxygen pickup during the high-temperature oxidation process of vanadium alloys remains a key issue, restricting their operation conditions and long service life. In a high-pressure oxygen environment, the main oxidation product V2O5, with a low melting point of ～680 ℃, is formed on the vanadium alloy surface, which cannot offer reliable protection to mitigate further oxidation over 650 ℃. However, despite being exposed to a very low-pressure oxygen environment, it is still unlikely for vanadium alloys to form an effective oxidation film to retard the oxygen absorption at temperatures over 450 ℃, mainly due to the high solubility of oxygen in vanadium. When the oxygen concentration reaches 0.2% in the matrix of V?4Cr?4Ti alloy, it can cause severe oxygen embrittlement, possibly due to oxygen accumulation and formation of fine oxidation precipitates at the grain boundaries and the adjacent matrix. Therefore, it is significantly important to enhance the high-temperature oxidation-resistant performance of the vanadium alloy to broaden the operation conditions. In this work, this research progress on the high-temperature oxidation resistance of vanadium alloys is systematically reviewed. In summary, three main methods for enhancing the oxidation–corrosion resistance of vanadium alloys at elevated temperatures are elaborated, i.e., oxidation-resistant element addition, diffusion coating, and overlay coating. Additionally, the characteristics and existing problems of these methods and the responding examples are also analyzed and discussed in detail. In the first two methods, it is impossible to completely isolate the alloy substrate from the service environment; thus, the typical oxidation product V2O5 is easily formed in the high-pressure oxygen environment, leading to severe oxidation corrosion and embrittlement, especially at elevated temperatures. Expectedly, the dense overlay coating presents a greater potential application mainly because of the thorough protection from the service environment. Finally, the development trend in the modification and technical requirements of the advanced overlay coatings on high-performance oxidation resistance are prospected in this paper as per the practical application demands for vanadium alloys, aiming to provide a beneficial reference for further research.
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圖 7 不同涂層的V–4Cr–4Ti合金樣品在650 ℃空氣中氧化1 h的質量增加情況及氧化后的截面SEM形貌[69,72]. (a, a′)無涂層; (b, b′)VSi2涂層; (c, c′) V1-xCrxSi2涂層; (d, d′) V1-xTixSi2涂層
Figure 7. Mass gain and cross-sectional microstructure of V–4Cr–4Ti alloys without and with different coatings for isothermal exposure at 650 °C for 50 h in air[69,72]: (a, a′) bare sample; (b, b′) VSi2 coating; (c, c′) V1-xCrxSi2 coating; (d, d′) V1-xTixSi2 coating
圖 10 不同熱處理工藝下V?5Cr?5Ti合金表面滲Al涂層的截面SEM形貌和元素分布[76]. (a, a') 750 ℃, 1 h; (b, b') 850 ℃, 1 h; (c, c') 950 ℃, 1 h; (d, d') 1050 ℃, 1 h
Figure 10. Cross-sectional SEM micrographs and corresponding element depth profiles of the aluminized coatings on V?5Cr?5Ti alloy obtained under different heat treatment regimes[76]: (a, a') 750 ℃ for 1 h; (b, b') 850 ℃ for 1 h; (c, c') 950 ℃ for 1 h; (d, d') 1050 ℃ for 1 h
表 1 釩合金在不同聚變包層系統中的服役環境
Table 1. Oxidation issues of vanadium alloys for fusion applications
Exposure environment Applicable component in a fusion system Typical service condition Lithium Li-cooled blanket structure 400?750 ℃[37] Vacuum Plasma facing component ～1×10?6 Pa[38] Helium He-cooled blanket structure 350?650 ℃, 18 MPa[36] Water Component with water cooling High-temperature pressurized water, 200?300 ℃[39] Air Vacuum component safety under leakage Operation temperature, ～600 ℃[40] 
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