{"title":"镁离子在断裂腐蚀条件下改变氧化物在锆合金上生长速度的作用","authors":"","doi":"10.1016/j.jnucmat.2024.155348","DOIUrl":null,"url":null,"abstract":"<div><p>General corrosion of nuclear reactor in core material like Zircaloy-2 and breakaway corrosion in particular are of great importance in ensuring its smooth long term operation. Metal ions like Mg<sup>2+</sup> added to the coolant, to mitigate corrosion of other structural materials like Carbon steel, can get incorporated in the corrosion product oxide on Zircaloy-2 and alter its corrosion behavior. Plasma Electrolytic Oxidation (PEO) method was employed to investigate the effect of Mg<sup>2+</sup> ions during breakaway corrosion of Zircaloy-2. The main objective was to understand the morphology, protectiveness, semiconducting properties of the Mg modified oxide films on Zircaloy-2 surface. DC potentials 300, 400 and 500 V were used to accelerate corrosion kinetics and form oxide mimicking the breakaway corrosion regime. Borate buffer (pH 9.8) was used as the electrolyte, and Mg acetate was added as Mg source for probing the effect of Mg<sup>2+</sup> ions. Oxide morphology depended largely on the formation potentials. The presence of magnesium resulted in thinner oxides with lower defect densities. GIXRD of the oxide showed stabilization of tetragonal phase in presence of Mg at 300 and 400 V. Oxide resistance and charge transfer resistances measured by EIS were observed to be higher due to Mg incorporation at these potentials. Mg addition facilitated formation of t-ZrO<sub>2</sub>. The electrochemical measurements suggested that the presence of Mg in ZrO<sub>2</sub> could reduce the connected porosity in the oxide thereby stifling the diffusion paths. These factors lead to improved corrosion protectiveness of the oxide formed in the presence of Mg.</p></div>","PeriodicalId":373,"journal":{"name":"Journal of Nuclear Materials","volume":null,"pages":null},"PeriodicalIF":2.8000,"publicationDate":"2024-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Role of magnesium ions in modifying oxide growth rate on Zircaloy under breakaway corrosion regimes\",\"authors\":\"\",\"doi\":\"10.1016/j.jnucmat.2024.155348\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>General corrosion of nuclear reactor in core material like Zircaloy-2 and breakaway corrosion in particular are of great importance in ensuring its smooth long term operation. Metal ions like Mg<sup>2+</sup> added to the coolant, to mitigate corrosion of other structural materials like Carbon steel, can get incorporated in the corrosion product oxide on Zircaloy-2 and alter its corrosion behavior. Plasma Electrolytic Oxidation (PEO) method was employed to investigate the effect of Mg<sup>2+</sup> ions during breakaway corrosion of Zircaloy-2. The main objective was to understand the morphology, protectiveness, semiconducting properties of the Mg modified oxide films on Zircaloy-2 surface. DC potentials 300, 400 and 500 V were used to accelerate corrosion kinetics and form oxide mimicking the breakaway corrosion regime. Borate buffer (pH 9.8) was used as the electrolyte, and Mg acetate was added as Mg source for probing the effect of Mg<sup>2+</sup> ions. Oxide morphology depended largely on the formation potentials. The presence of magnesium resulted in thinner oxides with lower defect densities. GIXRD of the oxide showed stabilization of tetragonal phase in presence of Mg at 300 and 400 V. Oxide resistance and charge transfer resistances measured by EIS were observed to be higher due to Mg incorporation at these potentials. Mg addition facilitated formation of t-ZrO<sub>2</sub>. The electrochemical measurements suggested that the presence of Mg in ZrO<sub>2</sub> could reduce the connected porosity in the oxide thereby stifling the diffusion paths. These factors lead to improved corrosion protectiveness of the oxide formed in the presence of Mg.</p></div>\",\"PeriodicalId\":373,\"journal\":{\"name\":\"Journal of Nuclear Materials\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.8000,\"publicationDate\":\"2024-08-15\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Nuclear Materials\",\"FirstCategoryId\":\"5\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0022311524004495\",\"RegionNum\":2,\"RegionCategory\":\"工程技术\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"MATERIALS SCIENCE, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Nuclear Materials","FirstCategoryId":"5","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0022311524004495","RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
摘要
核反应堆堆芯材料(如锆合金-2)的一般腐蚀,特别是断裂腐蚀,对确保其长期平稳运行至关重要。为减轻碳钢等其他结构材料的腐蚀而添加到冷却剂中的金属离子(如 Mg2+)会融入 Zircaloy-2 上的腐蚀产物氧化物中,并改变其腐蚀行为。为了研究 Mg2+ 离子在 Zircaloy-2 断裂腐蚀过程中的影响,采用了等离子电解氧化(PEO)方法。主要目的是了解 Zircaloy-2 表面镁修饰氧化物薄膜的形态、保护性和半导体特性。使用直流电位 300、400 和 500 V 加速腐蚀动力学,并形成模拟脱离腐蚀机制的氧化物。电解液采用硼酸盐缓冲液(pH 值为 9.8),并添加醋酸镁作为镁源,以探测 Mg2+ 离子的影响。氧化物的形态在很大程度上取决于形成电位。镁的存在使氧化物更薄,缺陷密度更低。氧化物的 GIXRD 显示,在 300 V 和 400 V 电压下,镁的存在使四方相稳定。在这些电位下,通过 EIS 测量到的氧化物电阻和电荷转移电阻因加入镁而升高。镁的加入促进了 t-ZrO2 的形成。电化学测量结果表明,ZrO2 中镁的存在可降低氧化物中的连通孔隙率,从而抑制扩散路径。这些因素提高了在镁存在下形成的氧化物的腐蚀保护性。
Role of magnesium ions in modifying oxide growth rate on Zircaloy under breakaway corrosion regimes
General corrosion of nuclear reactor in core material like Zircaloy-2 and breakaway corrosion in particular are of great importance in ensuring its smooth long term operation. Metal ions like Mg2+ added to the coolant, to mitigate corrosion of other structural materials like Carbon steel, can get incorporated in the corrosion product oxide on Zircaloy-2 and alter its corrosion behavior. Plasma Electrolytic Oxidation (PEO) method was employed to investigate the effect of Mg2+ ions during breakaway corrosion of Zircaloy-2. The main objective was to understand the morphology, protectiveness, semiconducting properties of the Mg modified oxide films on Zircaloy-2 surface. DC potentials 300, 400 and 500 V were used to accelerate corrosion kinetics and form oxide mimicking the breakaway corrosion regime. Borate buffer (pH 9.8) was used as the electrolyte, and Mg acetate was added as Mg source for probing the effect of Mg2+ ions. Oxide morphology depended largely on the formation potentials. The presence of magnesium resulted in thinner oxides with lower defect densities. GIXRD of the oxide showed stabilization of tetragonal phase in presence of Mg at 300 and 400 V. Oxide resistance and charge transfer resistances measured by EIS were observed to be higher due to Mg incorporation at these potentials. Mg addition facilitated formation of t-ZrO2. The electrochemical measurements suggested that the presence of Mg in ZrO2 could reduce the connected porosity in the oxide thereby stifling the diffusion paths. These factors lead to improved corrosion protectiveness of the oxide formed in the presence of Mg.
期刊介绍:
The Journal of Nuclear Materials publishes high quality papers in materials research for nuclear applications, primarily fission reactors, fusion reactors, and similar environments including radiation areas of charged particle accelerators. Both original research and critical review papers covering experimental, theoretical, and computational aspects of either fundamental or applied nature are welcome.
The breadth of the field is such that a wide range of processes and properties in the field of materials science and engineering is of interest to the readership, spanning atom-scale processes, microstructures, thermodynamics, mechanical properties, physical properties, and corrosion, for example.
Topics covered by JNM
Fission reactor materials, including fuels, cladding, core structures, pressure vessels, coolant interactions with materials, moderator and control components, fission product behavior.
Materials aspects of the entire fuel cycle.
Materials aspects of the actinides and their compounds.
Performance of nuclear waste materials; materials aspects of the immobilization of wastes.
Fusion reactor materials, including first walls, blankets, insulators and magnets.
Neutron and charged particle radiation effects in materials, including defects, transmutations, microstructures, phase changes and macroscopic properties.
Interaction of plasmas, ion beams, electron beams and electromagnetic radiation with materials relevant to nuclear systems.