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Zr-1Sn-0.35Fe-0.15Cr-0.10Nb-0.03Ge合金在400 ℃含氧过热蒸汽中的腐蚀行为
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1.上海大学材料研究所;2.上海大学微结构重点实验室

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国家自然科学基金资助(项目号51871141)


Corrosion behavior of Zr-1Sn-0.35Fe-0.15Cr-0.10Nb-0.03Ge alloy in 400℃ super-heated steam with oxygen
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1.Institute of Materials,Shanghai University;2.Laboratory for Microstructures,Shanghai University

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    摘要:

    为了探究Zr-1Sn-0.35Fe-0.15Cr-0.10Nb-0.03Ge(质量分数,%)合金在400 ℃/10.3 MPa不同氧含量过热蒸汽中的腐蚀行为,将Zr-1Sn-0.35Fe-0.15Cr-0.10Nb-0.03Ge合金样品分别放入静态高压釜和动态高压釜中进行400 ℃/10.3MPa的除氧、300 ppb 溶解氧(DO)和1000 ppb DO过热蒸汽腐蚀试验。采用扫描电子显微镜、透射电子显微镜、X射线光电子能谱等表征手段对合金和氧化膜的显微组织以及氧化膜中各元素的价态进行分析。结果表明,与除氧环境相比,Zr-1Sn-0.35Fe-0.15Cr-0.10Nb-0.03Ge合金在300 ppb DO和1000 ppb DO环境中的平均腐蚀速率分别增加了23.5%和29.4%,这说明DO会加速合金的腐蚀,且DO含量越高腐蚀加速作用越明显;DO不但促进了氧化膜中Fe、Cr、Sn和Ge等合金元素的氧化,还会加速O/M界面处Zr→ZrOx→ZrO2的演化过程; 基于以上两个方面提出了一种DO加速锆合金在400 ℃/10.3 MPa过热蒸汽中腐蚀的机制:腐蚀环境中DO含量的增加导致氧化膜中参与反应的O2-和OH-的浓度增加,这一方面加速了氧化膜中合金元素的氧化,导致氧化膜中缺陷浓度增加和局部附加应力增大;另一方面加速了O/M界面处Zr→ZrOx→ZrO2的演化,使O/M界面处产生更大的应力,提供更短的应力驰豫时间。这两方面的作用都会促进氧化膜中孔隙、裂纹等缺陷的生成,加速O2-和OH-的扩散,进而加速了合金的腐蚀。

    Abstract:

    In order to explore the corrosion behavior of Zr-1Sn-0.35Fe-0.15Cr-0.10Nb-0.03Ge (mass fraction, %) alloy in 400 ℃ super-heated steam with different oxygen contents, Zr-1Sn-0.35Fe-0.15Cr-0.10Nb-0.03Ge alloy specimens were put into static autoclave and dynamic autoclave for super-heated steam corrosion tests under deaeration, 300 ppb dissolved oxygen (DO) and 1000 ppb DO environment at 400 °C/10.3 MPa, respectively. The scanning electron microscope, transmission electron microscope, X-ray photoelectron spectroscope were used to characterize the microstructure of alloys and oxide films, as well as the valence state of the alloying element. Results show that compared with the deaeration environment, the average corrosion rate of Zr-1Sn-0.35Fe-0.15Cr-0.10Nb-0.03Ge alloy in 300 ppb DO and 1000 ppb DO environments increases by 23.5% and 29.4%, respectively, indicating that DO can accelerate the corrosion of the alloys, and the higher the DO content, the more obvious the corrosion acceleration effect. DO not only promotes the oxidation of Fe, Cr, Sn and Ge in the oxide film, but also accelerates the reaction process of Zr→ZrOx→ZrO2 in the transition layer at the O/M interface. Based on the above two aspects, a mechanism of DO accelerating the corrosion of zirconium alloys at 400 °C/10.3 MPa is proposed: The increase in DO content in the corrosive environment leads to an increase in the concentration of O2- and OH- participating in the reaction in the oxide film. On one hand, this promotes the oxidation of alloying elements, leading to the increase of defects in number and local stress in the oxide film; on the other hand, this also accelerates the evolution of Zr→ZrOx→ZrO2 at the O/M interface, resulting in higher stress in the oxide film and providing less time for stress release during oxidation. The roles of the two aspects both promote the generation of pores and cracks, and accelerate the diffusion of O2- and OH-, thus accelerate the corrosion of zirconium alloys.

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徐诗彤,姚美意,白勇,黄建松,林晓冬,胡丽娟,谢耀平,梁雪,彭剑超,徐静,周邦新. Zr-1Sn-0.35Fe-0.15Cr-0.10Nb-0.03Ge合金在400 ℃含氧过热蒸汽中的腐蚀行为[J].稀有金属材料与工程,2023,52(5):1746~1758.[Xu Shitong, Yao Meiyi, Bai Yong, Huang Jiansong, Lin Xiaodong, Hu Lijuan, Xie Yaoping, Liang Xue, Peng Jianchao, Xu Jing, Zhou Bangxin. Corrosion behavior of Zr-1Sn-0.35Fe-0.15Cr-0.10Nb-0.03Ge alloy in 400℃ super-heated steam with oxygen[J]. Rare Metal Materials and Engineering,2023,52(5):1746~1758.]
DOI:10.12442/j. issn.1002-185X.20220229

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  • 收稿日期:2022-03-22
  • 最后修改日期:2022-06-10
  • 录用日期:2022-06-13
  • 在线发布日期: 2023-06-08
  • 出版日期: 2023-05-29