一回路注锌对镍基690合金管腐蚀及腐蚀产物释放的影响

Effect of Zinc Addition on Corrosion and Metal Release Behavior of Nickel-based Alloy 690 in PWR Primary Water

  • 摘要: 在模拟压水堆(PWR)一回路注锌浓度分别为0、10、40 ppb的高温水中,对镍基690合金管开展了长达3 000 h的均匀腐蚀实验。采用失重法计算了其在不同阶段的腐蚀失重量和腐蚀产物释放量,获得了腐蚀动力学曲线,并计算了腐蚀速率和腐蚀产物释放速率。采用扫描电镜(SEM)及透射电镜(TEM)等方法分析了氧化膜表面形貌、截面厚度及元素分布。结果表明,10 ppb Zn的注入即可使镍基690合金管的平均腐蚀速率下降约18%,腐蚀产物释放速率下降约14%;增加Zn浓度至40 ppb后,平均腐蚀速率和释放速率进一步得到抑制,均下降约35%。微观分析表明冷却剂中的Zn通过置换和填充作用,在镍基690合金管表面形成低溶解度的Zn(Cr,Fe)2O4尖晶石,提高了氧化膜的稳定性与致密性,阻碍了金属离子向外扩散以及氧离子向内扩散,进而显著降低镍基690合金管的腐蚀速率和腐蚀产物释放速率。

     

    Abstract: The effect of Zn addition on general corrosion and metal release behavior of alloy 690 were investigated in simulated pressurized water reactor (PWR) primary water with 0, 10 and 40 ppb Zn additions. The corrosion rate and the metal release rate were calculated by weight loss method after3000 h exposure. The surface and cross-sectional morphology, thickness and element distribution along the oxide film were analyzed by scanning electron microscope (SEM) and transmission electron microscope-energy disperse spectroscopy (TEM-EDS). The crystallographic structure of the outer and inner oxides was identified using atomic-resolution TEM imaging with fast Fourier transformation (FFT). The results indicate that the corrosion rate, metal release rate and oxide film thickness of alloy 690 all decreased with the increase in Zn concentrations. The addition of 10 ppb Zn results in an approximately 18% reduction in the average corrosion rate and 14% reduction in the metal release rate, which further decreases by about 35% with an increase in Zn concentration to 40 ppb. Meanwhile, the average thickness of oxide film of alloy 690 significantly decreases from 110 nm to 25 nm when the concentration of Zn is increased from 0 to 40 ppb. The microstructural analysis of the oxide film indicates that the oxide film of alloy 690 exhibits a three-layer structure in 40 ppb Zn addition condition. The outermost oxide film has less Zn and is primarily composed of (Zn, Ni)Fe2O4. The intermediate oxide film contains much more Zn with a structure of Zn(Cr, Fe)2O4. The innermost oxide film at the oxide/metal (O/M) interface is mainly composed of Cr2O3. In PWR primary water, the free energy required for the formation of spinel ZnCr2O4 is lower than that of FeCr2O4 and NiCr2O4, and ZnCr2O4 exhibits a much lower solubility compared to other spinel, which results in its greater stability within the oxidation film. Meanwhile the Zn2+ promotes the denser Zn(Cr,Fe)2O4 outer and intermediate oxide film formation by filling the cation vacancies and replacing the Ni2+ and Fe2+ in spinel. In summary, the Zn addition can significantly enhance the stability and compactness of the oxide film on alloy 690, thereby retarding the outward diffusion of metal ions and inward diffusion of oxygen ions. Additionally, it reduces the oxygen partial pressure at the O/M interface, promoting the formation of an inner layer composed of Cr2O3. Consequently, this effectively suppresses corrosion and minimizes metal release from alloy 690 in PWR environments.

     

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