纳米晶Ni-12Cr合金800 ℃高温氧化动力学和氧化膜结构演化

doi:10.11902/1005.4537.2022.052

中国腐蚀与防护学报

2022, Vol. 42

Issue (5): 733-742 DOI: 10.11902/1005.4537.2022.052

研究报告

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纳米晶Ni-12Cr合金800 ℃高温氧化动力学和氧化膜结构演化

张勤¹, 梁涛沙², 王文², 赵朗朗¹, 姜岳峰¹(

)

^1.中核四0四有限公司兰州 732850
^2.中国科学院金属研究所沈阳材料科学国家研究中心沈阳 110016

Oxidation Kinetics and Microstructure Evolution of Nanocrystalline Ni-12Cr Alloy at 800 ℃

ZHANG Qin¹, LIANG Taosha², WANG Wen², ZHAO Langlang¹, JIANG Yuefeng¹(

)

^1.The 404 Company Limited, China National Nuclear Corporation, Lanzhou 732850, China
^2.Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China

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摘要:

利用聚焦离子束扫描电镜和扫描透射电镜研究了粗晶和纳米晶结构的Ni-12Cr合金在800 ℃空气中氧化的动力学行为和氧化膜的结构演化。结果表明,氧化初期25 s时,粗晶和纳米晶的氧化膜均为外层NiO和内层富Cr的双层结构。随着氧化的进行,粗晶氧化膜演化为NiO/ (NiO+NiCr₂O₄) /疏松Cr₂O₃/内氧化层的多层结构；而纳米晶发生了Cr的选择性氧化,形成了保护性Cr₂O₃膜,Cr₂O₃以非晶晶化的方式形核生长；纳米晶保护性氧化膜的形成早于纳米晶粒的粗化。根据有效扩散系数修正的Wagner理论,Ni-12Cr合金在800 ℃发生由内氧化向外氧化转变的临界晶粒尺寸约为94 nm。纳米晶的氧化动力学曲线分为两个阶段,转折点约为氧化1 h。两阶段均符合抛物线规律,抛物线速率常数k_p分别为1.76×10^-13和1.58×10^-14 cm²·s^-1。

关键词 ：纳米晶, Ni-Cr合金, 高温氧化, 选择性氧化

Abstract：

Nanocrystallization can increase the diffusion rate of alloying elements, such as Cr, Al, and then improve the high-temperature oxidation resistance of metallic alloys due to the presence of high-volume fraction of grain boundaries. Up to now, the studies on the effect of nano-structure on the oxidation behavior of alloys mainly focus on the oxidation kinetics and the structure of oxide scale at steady stage. The microstructure of oxide scale formed on nano-structured alloys during oxidation, especially at the initial stage, is lack of characterization. At the same time, nano-structured alloys are far away from thermodynamic equilibrium state, which inevitably result in the grain coarsening during oxidation process. Therefore, it is necessary to characterize the microstructure of oxide scale on nano-structured alloys to understand the relationship between grain coarsening of alloy and the formation of oxide scale on its surface. In this study, the oxidation behavior of coarse-grained (CG) and nanocrystalline (NC) Ni-12Cr alloys (mass fraction in nominal chemical composition) at 800 ℃ in air were studied. The NC alloy was prepared by severe plastic deformation, and the average grain size is around 42 nm. Focused ion beam (FIB) microscope and scanning transmission electron microscope (STEM) were used to characterize the microstructure and composition distribution of the scale. The results demonstrate that a two-layered scale, external NiO and internal Cr-rich layer, is formed on both of CG and NC alloys after oxidation for 25 s. The scale on CG alloy develops into a multilayered structure, which includes NiO/(NiO+NiCr₂O₄)/porous Cr₂O₃/internal oxidation zone after oxidation for 10 min, while the Cr-rich layer on NC alloy crystallizes and forms a protective Cr₂O₃ scale after oxidation for 2 min. The oxidation kinetics of NC alloy consists of two stages, both of which follow the parabolic law. The parabolic rate constants of the two stages are 1.76×10^-13 cm²·s^-1 (within 1 h) and 1.58×10^-14 cm²·s^-1 (1-109 h) respectively, both of which are about 3-4 orders of magnitude lower than that of CG alloy. The study on grain growth kinetics of alloy indicates that the protective chromia scale forms before the significant coarsening of nano-grain. According to Wagner theory with the effective diffusion coefficient, the critical grain size for Ni-12Cr alloy to change from internal oxidation to external oxidation is about 94 nm at 800 ℃.

Key words： Nanocrystalline Ni-Cr alloy high temperature oxidation selective oxidation

收稿日期: 2022-03-01

ZTFLH:

TG174

基金资助:国家自然科学基金(52101107);中国博士后科学基金(2021M703274);中核集团2021年青年英才科研项目(75)

通讯作者: 姜岳峰 E-mail: jiangyfd@mail.ustc.edu.cn

Corresponding author: JIANG Yuefeng E-mail: jiangyfd@mail.ustc.edu.cn

作者简介: 张勤,女,1989年生,博士,工程师
梁涛沙,女,1991年生,博士,助理研究员

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引用本文:

张勤, 梁涛沙, 王文, 赵朗朗, 姜岳峰. 纳米晶Ni-12Cr合金800 ℃高温氧化动力学和氧化膜结构演化[J]. 中国腐蚀与防护学报, 2022, 42(5): 733-742.
Qin ZHANG, Taosha LIANG, Wen WANG, Langlang ZHAO, Yuefeng JIANG. Oxidation Kinetics and Microstructure Evolution of Nanocrystalline Ni-12Cr Alloy at 800 ℃. Journal of Chinese Society for Corrosion and protection, 2022, 42(5): 733-742.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2022.052 或 https://www.jcscp.org/CN/Y2022/V42/I5/733

图1 变形态Ni-12Cr合金微观组织

图2 粗晶和纳米晶结构Ni-12Cr合金在800 ℃空气中氧化109 h的氧化动力学曲线和抛物线速率常数

图3 粗晶Ni-12Cr合金在800 ℃下空气中氧化不同时间截面形貌

图4 粗晶在800 ℃空气中氧化25 s截面TEM形貌和EDS分析结果

图5 粗晶样品在800 ℃空气中氧化10 min后的截面TEM形貌、选区电子/纳米束衍射和EDS分析结果

图6 纳米晶在800 ℃空气中氧化25 s氧化膜截面形貌、纳米束衍射和元素分布图

图7 纳米晶在800 ℃空气中氧化2 min氧化膜截面形貌、纳米束衍射和元素分布图

图8 纳米晶在800 ℃空气中氧化1 h氧化膜截面形貌和元素分布图

图9 纳米晶在800 ℃空气中氧化10 h氧化膜截面形貌和元素分布图

图10 纳米晶Ni-12Cr合金在800 °C下保温不同时间后的晶粒尺寸分布

图11 粗晶和纳米晶Ni-12Cr合金 (800 ℃) 与纯Ni (800 ℃)[31]、粗晶Ni-20Cr合金 (800~1000 ℃)[19,32]氧化的抛物线速率常数对比

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