Zr-Nb合金包壳管氧化膜的微观结构
Microstructure of Zr-Nb Alloy Cladding Oxide Flim
摘 要
针对某Zr-Nb系合金包壳管水侧腐蚀，通过光学显微镜、X射线衍射分析（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）等技术，研究了Zr-Nb合金包壳管氧化膜的微观结构。结果表明：腐蚀生成的氧化膜表面分布有不同取向的微裂纹，其中垂直裂纹可以为氧离子的扩散提供快速路径。TEM分析表明氧化膜主要由柱状和等轴状单斜相ZrO2组成，基体/氧化膜界面附近等轴状单斜相ZrO2的存在与裂纹、大晶粒尺寸和晶内孪晶密切相关，导致ZrO2发生由四方相到单斜相的转变，由于残余应力导致的晶格膨胀，单斜相ZrO2晶面间距增加了约0.4%。
氧化膜
裂纹
晶体结构
Zr-Nb alloy
oxide flim
crack
crystal structure
Abstract
The microstructure of the oxide film of Zr-Nb alloy cladding was studied by optical microscopy, X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM). The results showed that microcracks with different orientations were distributed on the surface of the oxide film of Zr-Nb alloy, including vertical and transverse cracks. The vertical cracks could provide a fast path for the diffusion of oxygen ions. TEM results showed that the oxide film was mainly composed of columnar and equiaxed monoclinic ZrO2, The existence of equiaxed monoclinic ZrO2 grains near the interface of zirconium alloy matrix/oxide film was closely related to cracks, large grain size and intragranular twinning. Due to the lattice expansion caused by residual stress, the interplanar spacing of monoclinic ZrO2 increased about 0.4%.
中图分类号 TL341 DOI 10.11973/fsyfh-202207011
所属栏目 试验研究
基金项目 中核集团青年英才基金（FY202307000520）
收稿日期 2022/4/25
修改稿日期
网络出版日期
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引用该论文: WANG Huacai,CHENG Huanlin,GUO Lina,TANG Qi,HAN Hua. Microstructure of Zr-Nb Alloy Cladding Oxide Flim[J]. Corrosion & Protection, 2022, 43(7): 67
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参考文献
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【2】HONG J D, KIM H C, KIM J S, et al. Delayed hydride cracking assessment of PWR spent fuel during dry storage[J]. Nuclear Engineering and Design, 2017, 322:324-330.
【3】WANG Z, ZHOU B X, CHEN B, et al. In-situ oxidation and short-time corrosion investigation on strain and dislocation during the generation and growth of ZrO2[J]. Corrosion Science, 2017, 122:26-31.
【4】HARLOW W, GHASSEMI H, TAHERI M L. Determination of the initial oxidation behavior of zircaloy-4 by in situ TEM[J]. Journal of Nuclear Materials, 2016, 474:126-133.
【5】SHIBATA A, KATO Y, TAGUCHI T, et al. Corrosion properties of zircaloy-4 and M5 under simulated PWR water conditions[J]. Nuclear Technology, 2016, 196(1):89-99.
【6】VERLET R, TUPIN M, BALDACCHINO G, et al. Influence of light ion irradiation of the oxide layer on the oxidation rate of Zircaloy-4[J]. Corrosion Science, 2015, 98:327-338.
【7】YILMAZBAYHAN A, BREVAL E, MOTTA A T, et al. Transmission electron microscopy examination of oxide layers formed on Zr alloys[J]. Journal of Nuclear Materials, 2006, 349(3):265-281.
【8】白若玉, 高阳, 梁雪, 等. 国产ZIRLO合金动态水腐蚀氧化膜微观研究[J]. 原子能科学技术, 2020, 54(12):2461-2468.
【9】GARNER A, HU J, HARTE A, et al. The effect of Sn concentration on oxide texture and microstructure formation in zirconium alloys[J]. Acta Materialia, 2015, 99:259-272.
【10】CISZAK C, MERMOUX M, MIRO S, et al. Micro-Raman analysis of the fuel-cladding interface in a high burnup PWR fuel rod[J]. Journal of Nuclear Materials, 2017, 495:392-404.
【11】HU J, GARNER A, FRANKEL P, et al. Effect of neutron and ion irradiation on the metal matrix and oxide corrosion layer on Zr-1.0Nb cladding alloys[J]. Acta Materialia, 2019, 173:313-326.
【12】CHOLLET M, VALANCE S, ABOLHASSANI S, et al. Synchrotron X-ray diffraction investigations on strains in the oxide layer of an irradiated Zircaloy fuel cladding[J]. Journal of Nuclear Materials, 2017, 488:181-190.
【13】刘建章. 核结构材料[M]. 北京:化学工业出版社, 2007:41-46.
【14】TEJLAND P, ANDRÉN H O. Origin and effect of lateral cracks in oxide scales formed on zirconium alloys[J]. Journal of Nuclear Materials, 2012, 430(1/2/3):64-71.
【15】LIAO J J, YANG Z B, QIU S Y, et al. The correlation between tetragonal phase and the undulated metal/oxide interface in the oxide films of zirconium alloys[J]. Journal of Nuclear Materials, 2019, 524:101-110.
【16】CHOUDHURI G, MISHRA P, BASU S, et al. Effect of ion and neutron irradiation on oxide of PHWR fuel tube material[J]. Journal of Nuclear Materials, 2019, 514:12-27.
【17】ABOLHASSANI S, RESTANI R, REBAC T, et al. TEM examinations of the metal-oxide interface of zirconium based alloys irradiated in a pressurized water reactor[J]. Journal of ASTM International, 2005, 2(6):12390.
【18】LOZANOPEREZ S. Study of oxidation mechanisms of zirconium alloys by electron microscopy[J]. Oxford University, 2011:82-138.
【19】YARDLEY S S, MOORE K L, NI N, et al. An investigation of the oxidation behaviour of zirconium alloys using isotopic tracers and high resolution SIMS[J]. Journal of Nuclear Materials, 2013, 443(1/2/3):436-443.
【20】KIM H G, JEONG Y H, KIM T H. Effect of isothermal annealing on the corrosion behavior of Zr-xNb alloys[J]. Journal of Nuclear Materials, 2004, 326(2/3):125-131.
【21】YILMAZBAYHAN A, MOTTA A T, COMSTOCK R J, et al. Structure of zirconium alloy oxides formed in pure water studied with synchrotron radiation and optical microscopy:relation to corrosion rate[J]. Journal of Nuclear Materials, 2004, 324(1):6-22.
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【24】UNE K, TAKAGI I, SAWADA K, et al. Effect of proton irradiation on deuterium diffusion in zirconium oxide layer[J]. Journal of Nuclear Materials, 2012, 420(1/2/3):445-451.
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