Study on Corrosion Behavior of High-corrosion Resistance AFAs in Supercritical Water
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摘要: 为解决传统不锈钢在超临界水冷堆（SCWR）堆芯高温高压、强腐蚀性服役环境中不适用的问题，针对性地设计制备了新型含铝奥氏体不锈钢（AFAs），采用高压釜浸泡试验研究了其在600℃/25 MPa超临界水中的腐蚀行为。利用多种先进微观分析技术研究了AFAs在超临界水中腐蚀后试样表面氧化膜形貌、成分及结构特征，用以探究合金在超临界水中的耐腐蚀机制及氧化铝成膜行为。研究结果表明：AFAs在600℃超临界水中能形成连续的氧化铝膜从而具备优异的耐腐蚀性能，1000 h腐蚀增重量低于10 mg/dm2，优于文献报道的在相同条件下腐蚀的C276合金和310-ODS合金。该氧化铝膜与合金基体结合紧密无明显分界，能有效阻碍超临界水中氧化介质与合金基体的直接接触，抑制合金中Fe的外扩散，为合金提供优异的保护性。然而，AFAs中的Laves相会影响局部氧化铝膜的均匀性，导致外层MnCr2O4颗粒的形成。因此，AFAs需要在维持氧化铝连续成膜的同时严格控制Laves相含量，从而满足SCWR的应用需求。本文研究结果可为SCWR用含铝奥氏体不锈钢研发设计提供数据及理论支撑。
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关键词:
- 超临界水冷堆（SCWR） /
- 含铝奥氏体不锈钢（AFAs） /
- 均匀腐蚀 /
- 氧化铝膜 /
- Laves相
Abstract: To address the inapplicability of traditional stainless steel in the high-temperature, high-pressure and highly corrosive service conditions of supercritical-water cooled reactor core, a novel alumina-forming austenitic stainless steels (AFAs) was designed and prepared, and its corrosion behavior in supercritical water at 600℃/25 MPa was studied by autoclave immersion test. The morphology, composition and structural characteristics of the oxide scale on the surface of AFAs after corrosion in supercritical water were studied by using a variety of advanced micro-analysis techniques to explore the corrosion resistance mechanism of the alloy in supercritical water and the scale-forming behavior of alumina. The results show that the AFAs offered excellent corrosion resistance by forming a continuous alumina scale in supercritical-water at 600℃, with a corrosion weight gain of less than 10 mg/dm2 after 1000 h of exposure, which is better than that of C276 and 310-ODS alloys corroded under the same conditions reported in the literature. The alumina scale is densely and tightly combined with the alloy matrix without obvious separations, effectively hindering the direct contact between the oxidizing media and the alloy matrix, and inhibiting the external diffusion of Fe in the alloy, thus providing excellent protection for the alloy. However, the Laves in the AFAs can affect the uniformity of the localized alumina scale, leading to the formation of MnCr2O4 particles. Therefore, AFAs need to maintain continuous formation of alumina scale while strictly controlling the Laves phase level to satisfy the requirements of supercritical water-cooled reactor applications. The results of this paper can provide data and theoretical support for the development and design of aluminum-forming austenitic stainless steels for supercritical water-cooled reactors. -
图 2 AFAs在600℃/25 MPa超临界水中腐蚀1000 h的腐蚀增重-时间曲线
Figure 2. Corrosion Weight Gain versus Time Curves of AFAs Exposed in 600℃ and 25 MPa Supercritical Water
图 3 AFAs在600℃/25 MPa超临界水中腐蚀100、1000 h后表面氧化膜形貌
Figure 3. Surface Oxide Morphologies of AFAs Exposed in 600℃ and 25 MPa Supercritical-water for 100 h and 1000 h
图 4 AFAs在600℃超临界水中腐蚀100 h和1000 h后表面氧化物物相分析
Figure 4. Surface Oxide Analysis of AFAs Exposed in 600℃ Supercritical-water for 100 h and 1000 h
图 5 AFAs在600℃超临界水中腐蚀1000 h后截面氧化膜EDS面扫描分析
Figure 5. EDS Mapping Analysis of the Cross-sectional Oxide Formed on AFAs Exposed in 600℃ Supercritical-water for 1000 h
图 6 AFAs在600℃超临界水中腐蚀1000 h后的截面氧化膜线扫描分析结果（线扫描位置见图5）
Figure 6. EDS Line Analysis of the Cross-sectional Oxide Formed on AFAs Exposed in 600℃ Supercritical-water for 1000 h
图 7 AFAs在600℃超临界水中腐蚀1000 h后截面氧化膜SAED表征
Figure 7. SAED Analysis of Cross-sectional Oxide Formed on AFAs Exposed in 600℃ Supercritical-water for 1000 h
图 8 AFAs在600℃超临界水中腐蚀1000 h后截面氧化膜微区分析
Figure 8. Detail Analysis of Cross-sectional Oxide Formed on AFAs Exposed in 600℃ Supercritical-water for 1000 h
图 9 AFAs在600℃超临界水中腐蚀1000 h后局部不连续氧化铝膜微区分析
Figure 9. Detail Analysis of Discontinuous Alumina Scale Formed on AFAs Exposed in 600℃ Supercritical-water for 1000 h
表 1 AFAs成分表
Table 1. Chemical Composition of AFAs
元素 Ni Cr Al Nb Cu Si Mn Mo C Fe 质量分数（理论）/% 26 19 2.5 1 1.5 1 2 4 0.08 余量 质量分数（实际）/% 25.63 19.50 2.21 0.82 1.59 1.26 2.00 3.40 0.08 余量 
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表 2 3种合金在超临界水中腐蚀动力学拟合结果
Table 2. Fitting Results of Corrosion Kinetics in Supercritical-water for Three Alloys
合金材料 k n R2 C276 1.54 0.46 0.98 310-ODS 8.10 0.18 0.97 AFAs 0.20 0.54 0.99
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位置 元素质量分数/% O Al Cr Fe Ni Mn Si Cu Nb Mo 1 29.36 6.51 31.30 15.58 8.34 6.19 0.44 0.41 0.62 1.27 2 25.86 15.10 19.69 19.38 6.73 7.59 1.04 0.60 0.48 3.51 3 16.35 5.48 19.49 31.46 17.39 4.13 0.90 0.93 0.73 3.14 4 25.70 3.96 32.85 19.32 9.62 4.80 0.82 0.47 0.50 1.96
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表 4 AFAs在600℃超临界水中发生的氧化反应及对应反应的形成能
Table 4. Reactions and Corresponding Gibbs Free Energy of AFAs Exposed in 600℃ Supercritical-water
反应 形成能ΔGf/(kJ·mol−1) $ 3\mathrm{F}\mathrm{e}+2{\mathrm{O}}_{2}\to {\mathrm{F}\mathrm{e}}_{3}{\mathrm{O}}_{4} $ $ -202.9 $ $ 2\mathrm{F}\mathrm{e}+3/2{\mathrm{O}}_{2}\to {\mathrm{F}\mathrm{e}}_{2}{\mathrm{O}}_{3} $ $ -126.6 $ $ \mathrm{N}\mathrm{i}+1/2{\mathrm{O}}_{2}\to \mathrm{N}\mathrm{i}\mathrm{O} $ $ -160.7 $ $ 2\mathrm{A}\mathrm{l}+3/2{\mathrm{O}}_{2}\to {\mathrm{A}\mathrm{l}}_{2}{\mathrm{O}}_{3} $ $ -454.2 $ $ 2\mathrm{C}\mathrm{r}+3/2{\mathrm{O}}_{2}\to {\mathrm{C}\mathrm{r}}_{2}{\mathrm{O}}_{3} $ $ -298.3 $ $ 2\mathrm{M}\mathrm{n}+{\mathrm{C}\mathrm{r}}_{2}{\mathrm{O}}_{3}\to \mathrm{M}\mathrm{n}{\mathrm{C}\mathrm{r}}_{2}{\mathrm{O}}_{4} $ $ -1224.9 $
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