第一壁自钝化<strong>W-Cr-Zr</strong>合金的氧化行为和氧化层结构

doi:10.11901/1005.3093.2024.211

材料研究学报

2025, Vol. 39

Issue (5): 343-352 DOI: 10.11901/1005.3093.2024.211

研究论文

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第一壁自钝化W-Cr-Zr合金的氧化行为和氧化层结构

吴玉程¹^,²(

), 左彤¹, 谭晓月¹^,², 朱晓勇¹^,², 刘家琴³^,⁴

^1.合肥工业大学材料科学与工程学院合肥 230009
^2.有色金属材料与加工国家地方工程研究中心合肥 230009
^3.合肥工业大学工业与装备研究院合肥 230009
^4.安徽省先进复合材料设计与应用工程中心合肥 230051

Oxidation Behavior of Self-passivated W-Cr-Zr Alloys as the First Wall Candidate Material

WU Yucheng¹^,²(

), ZUO Tong¹, TAN Xiaoyue¹^,², ZHU Xiaoyong¹^,², LIU Jiaqin³^,⁴

^1.School of Materials Science and Engineering, Hefei University of Technology, Hefei 230009, China
^2.National-Local Joint Research Center of Nonferrous Metals and Processing Technology, Hefei 230009, China
^3.Institute of Industry and Equipment, Hefei University of Technology, Hefei 230009, China
^4.Anhui Advanced Composite Material Design and Application Engineering Center, Hefei 230051, China

引用本文:

吴玉程, 左彤, 谭晓月, 朱晓勇, 刘家琴. 第一壁自钝化W-Cr-Zr合金的氧化行为和氧化层结构[J]. 材料研究学报, 2025, 39(5): 343-352.
Yucheng WU, Tong ZUO, Xiaoyue TAN, Xiaoyong ZHU, Jiaqin LIU. Oxidation Behavior of Self-passivated W-Cr-Zr Alloys as the First Wall Candidate Material[J]. Chinese Journal of Materials Research, 2025, 39(5): 343-352.

全文: PDF(24613 KB) HTML

摘要:

用3D激光测量显微镜、扫描电子显微镜(SEM)和X射线衍射仪(XRD)等手段表征自钝化W-Cr-Zr合金氧化前后表面的粗糙度、形貌和物相组成，研究了氧化层结构对其后续氧化行为的影响。结果表明，自钝化W-Cr-Zr合金氧化后表面的粗糙度越大表明其在氧化初期生成的氧化层裂纹越多。在后续的氧化过程中裂纹作为氧与基体接触的通道，使基体的氧化加速，从而使其线性氧化速率提高。W-Cr-Zr合金氧化后生成的氧化层最表面是高温稳定的Cr₂WO₆，亚表层是易升华的WO_2.83。除去氧化层中的Cr₂WO₆层后，在后续的氧化过程中基体的严重氧化和WO_2.83的迅速升华仍生成较为疏松的具有一定抗氧化性能的Cr₂WO₆层。

关键词 ：金属材料, 核聚变, W-Cr-Zr合金, 自钝化钨合金, 初始表面氧化层, 氧化行为

Abstract：

Self-passivating tungsten alloy (SPTA) inhibits the further oxidation by forming dense oxide scale on its surface. Therefore, the use of self-passivating tungsten alloys as the first wall candidate material for nuclear fusion is a material solution proposed to address the safety hazards that may arise in the event of loss-of-coolant accident in future nuclear fusion devices. The compact oxide scale formed on the surface of self-passivating tungsten alloys requires the participation of passivating elements, and their oxidation behavior is related to its composition and structure. Herein, an alloy W87.6-Cr11.4-Zr1.0 (in mass fraction) was prepared by mechanical alloying and field assisted sintering technology, then its oxidation behavior was assessed intermittently at 1000 ^oC in a flowing gas mixture Ar+20%O₂ (volume fraction). The surface roughness, morphology and phase composition of the W-Cr-Zr alloy before and after oxidation were characterized by 3D laser measurement microscopy, scanning electron microscope (SEM) and X-ray diffraction instrument (XRD), and the influence of oxide scale structure on the subsequent oxidation behavior of W-Cr-Zr alloy was investigated. The results show that the larger the surface roughness, the more cracks of the oxide scale formed in the initial oxidation stage. In the subsequent oxidation process, cracks act as the short-circuit channel for inward migration of oxygen to accelerate the oxidation of the underneath alloy substrate, thus having a large linear oxidation rate. The top layer of the oxide scale formed by the oxidation of W-Cr-Zr alloy is Cr₂WO₆ with high temperature stability, and the inner layer is WO_2.83 with easy sublimation. After the removal of the Cr₂WO₆ layer, a relatively loose Cr₂WO₆ layer can still grow in the subsequent oxidation process along with the severe oxidation of the matrix and the rapid sublimation of WO_2.83, which has certain protectiveness for the substrate. Therefore, to adjust or control the microstructure and oxidation behavior of the tungsten alloy is of great reference value for material selection and operation safety of nuclear fusion device components.

Key words： metallic materials nuclear fusion W-Cr-Zr alloy self-passivating tungsten alloy initial surface layer oxidation behavior

收稿日期: 2024-05-16

ZTFLH:

TL34

基金资助:国家自然科学基金国际(地区)合作与交流重点项目(52020105014);国家重点研发计划(2022YFE03140001);高等学校学科创新引智计划“清洁能源新材料与技术”(111 计划，B18018)

通讯作者: 吴玉程，ycwu@hfut.edu.cn，研究方向为能源材料及纳米功能材料

Corresponding author: WU Yucheng, Tel: (0551)62905985, E-mail: ycwu@hfut.edu.cn

作者简介: 吴玉程，男，1962年生，教授

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图1 W-Cr-Zr合金氧化前的显微组织、不同表面处理后样品的表面形貌和相应的线粗糙度

图2 表面粗糙度不同的W-Cr-Zr合金在1000 ℃氧化2 min后氧化层表面的形貌

图3 表面粗糙度不同的W-Cr-Zr合金在1000 ℃的氧化行为曲线和线性氧化速率与表面粗糙度的关系

图4 表面粗糙度不同的W-Cr-Zr合金在1000 ℃氧化20 h后的XRD谱

图5 表面粗糙度不同的W-Cr-Zr合金在1000 ℃氧化20 h后的表面形貌

图6 表面粗糙度不同的W-Cr-Zr合金在1000 ℃氧化20 h后氧化层的截面、氧化层厚度与样品氧化前表面粗糙度的关系以及样品氧化后的表面粗糙度

图7 W-Cr-Zr合金在1000 ℃氧化的氧化增重曲线(红线)和去除表面氧化物后的氧化增重曲线(蓝线)

图8 W-Cr-Zr合金氧化40 h后、去除最表层和再氧化40 h后的XRD谱

图9 W-Cr-Zr合金氧化40 h后的表面形貌、去除最表层氧化物后的形貌以及再氧化40 h后的表面形貌

图10 W-Cr-Zr合金氧化40 h后的截面、再氧化40 h后的截面以及相应的W、Cr和O的面扫描能谱

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