锆合金氧化膜中相变与裂纹演化的相场模拟

doi:10.11900/0412.1961.2023.00240

金属学报

2025, Vol. 61

Issue (7): 1082-1092 DOI: 10.11900/0412.1961.2023.00240

研究论文

本期目录 | 过刊浏览

锆合金氧化膜中相变与裂纹演化的相场模拟

王小齐¹^,², 张金虎¹^,²(

), 郭辉¹^,², 李学雄¹, 许海生¹^,², 柏春光¹^,², 徐东生¹^,²(

), 杨锐¹^,²

1 中国科学院金属研究所沈阳 110016
2 中国科学技术大学材料科学与工程学院沈阳 110016

Phase-Field Simulations of Phase Transformation and Crack Evolution in Zirconium Alloy Oxide Film

WANG Xiaoqi¹^,², ZHANG Jinhu¹^,²(

), GUO Hui¹^,², LI Xuexiong¹, XU Haisheng¹^,², BAI Chunguang¹^,², XU Dongsheng¹^,²(

), YANG Rui¹^,²

1 Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
2 School of Materials Science and Engineering, University of Science and Technology of China, Shenyang 110016, China

引用本文:

王小齐, 张金虎, 郭辉, 李学雄, 许海生, 柏春光, 徐东生, 杨锐. 锆合金氧化膜中相变与裂纹演化的相场模拟[J]. 金属学报, 2025, 61(7): 1082-1092.
Xiaoqi WANG, Jinhu ZHANG, Hui GUO, Xuexiong LI, Haisheng XU, Chunguang BAI, Dongsheng XU, Rui YANG. Phase-Field Simulations of Phase Transformation and Crack Evolution in Zirconium Alloy Oxide Film[J]. Acta Metall Sin, 2025, 61(7): 1082-1092.

全文: PDF(1628 KB) HTML

摘要:

锆合金因具有较低的热中子吸收截面、优良的耐腐蚀性能和力学性能，是轻水堆核电站中重要的核反应堆结构材料。然而，在高温及腐蚀条件下，锆合金表面会发生氧化腐蚀，当氧化膜厚度达2~3 μm时，其生长速率会急剧增大，即发生腐蚀动力学转变，限制了锆合金在反应堆中的使用寿命。本工作借助相场动力学方法对锆合金氧化膜中四方相ZrO₂ (t-ZrO₂)向单斜相ZrO₂ (m-ZrO₂)转变及氧化膜-金属体系中裂纹的扩展行为进行了研究。模拟结果表明，氧化膜中发生t-ZrO₂→m-ZrO₂转变时，生成的m-ZrO₂相呈“芒果状”且主要受压应力作用，而基体在沿m-ZrO₂晶粒的长轴和短轴方向上分别受到压应力和拉应力，且应力均随m-ZrO₂的长大而增大。应力下裂纹扩展模拟发现，氧化膜中平行于其与金属界面的横向裂纹，可在垂直于界面的拉伸应力作用下扩展，并可与邻近的横向裂纹及缺陷相互连接，形成缺陷层。氧化膜中垂直于界面的纵向裂纹在扩展至界面后未向金属基体中继续扩展，而是向氧化膜中产生分叉，其继续扩展将促进氧化层从基体上剥落。

关键词 ：锆合金, 相场法, 相变, 裂纹

Abstract：

Zirconium alloys are considered as important nuclear reactor structural materials owing to their low thermal neutron absorption cross-section, good corrosion resistance, and good mechanical properties in high-temperature and high-pressure water. However, under high temperature and corrosion conditions, an oxide film forms on the surface of zirconium alloys, and its growth rate increases rapidly when the thickness is 2-3 μm, leading to a transition in corrosion kinetics, which limits its service life in the reactor. In this study, the transformation of zirconia from tetragonal (t-ZrO₂) to monoclinic (m-ZrO₂) and the crack propagation behavior in the oxidation layer on zirconium alloys have been investigated using phase-field simulation. During the transformation of t-ZrO₂ to m-ZrO₂ in the oxide film, the t-ZrO₂ matrix undergoes compressive and tensile stresses along the long and short axes of the m-ZrO₂ precipitate, respectively, whereas the m-ZrO₂ precipitate primarily undergoes compressive stress during the transformation. Moreover, the stresses increase with the growth of the m-ZrO₂ grains. The simulations of crack evolution reveal that the cracks in the oxidation layer parallel to the oxide-metal interface expand under applied tensile stress perpendicular to the interface. Such cracks may connect with other isolated cracks and defects forming a defect layer. Upon extending to the oxide-metal interface, surface cracks perpendicular to the interface bifurcate in the oxide rather than penetrate into the metal matrix, which facilitates the peeling off of the oxidation layer from the substrate.

Key words： zircaloy phase-field method phase transformation crack

收稿日期: 2023-06-05

ZTFLH:

TG146.4

基金资助:国家重点研发计划项目(2021YFB3702604);中科院网信专项项目(CAS-WX2021PY-0103)

通讯作者: 徐东生，dsxu@imr.ac.cn，主要从事钛合金计算设计与工艺优化研究
张金虎，jinhuzhang@imr.ac.cn，主要从事钛基合金微观组织演变模拟研究

作者简介: 王小齐，男，1997年生，硕士生

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	许海生
	柏春光
	徐东生
	杨锐
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https://www.ams.org.cn/CN/10.11900/0412.1961.2023.00240 或 https://www.ams.org.cn/CN/Y2025/V61/I7/1082

Parameter	Symbol	Value
Chemical driving force	$Δ G$	36.8 × 10⁶ J·m^-3
Gradient energy coefficient	$k η$	1 × 10^-8 J·m^-1
Energy density coefficient	$a$	0.14
Energy density coefficient	$b$	12.42
Energy density coefficient	$c$	12.28
Kinetic coefficient	$L$	2 m³·J^-1·s^-1

表1 模拟计算中的相关参数[24]

Parameters	Symbol	Value
Young's modulus of t-ZrO₂	$E t$	212 GPa
Young's modulus of m-ZrO₂	$E m$	241 GPa
Poisson's ratio of t-ZrO₂	$ν t$	0.33
Poisson's ratio of m-ZrO₂	$ν m$	0.29
Eigenstrain of t-ZrO₂	$ε i j 0$ (t-ZrO₂)	$0.0049 0.0761 0.0761 0.0180$
Eigenstrain of m-ZrO₂	$ε i j 0$ (m-ZrO₂)	$0.0049 - 0.0761 - 0.0761 0.0180$
Eigenstrain of t-ZrO₂ (after 90° rotation about Y axis)	$ε i j 0'$ (t-ZrO₂)	$0 0.0761 0 0.0180$
Eigenstrain of m-ZrO₂ (after 90° rotation about Y axis)	$ε i j 0'$ (m-ZrO₂)	$0 - 0.0761 0 0.0180$

表2 弹性能计算所需相关参数[24]

图1 带核单晶相场模型示意图

图2 m-ZrO2晶粒长大过程中的形貌演化

图3 m-ZrO2晶粒长大过程中的应力分布演化

图4 绕Y轴旋转90°后m-ZrO2析出相的长大过程

图5 绕Y轴旋转90°后晶粒长大过程中的应力分布演化

图6 氧化膜中平行于氧化物-金属界面的裂纹示意图

图7 氧化膜中平行于氧化物-金属界面裂纹在扩展前后应力与场变量分布的相场模拟结果

图8 氧化膜中平行于氧化物-金属界面的裂纹演化模拟得到的拉伸力-位移曲线

图9 垂直于氧化物-金属界面的裂纹模型示意图

图10 相场模拟垂直氧化物-金属界面的裂纹演化

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