高<strong>Nb</strong>锆合金在含氧蒸汽中耐腐蚀性能恶化的机理

doi:10.11900/0412.1961.2022.00066

金属学报

2024, Vol. 60

Issue (4): 509-521 DOI: 10.11900/0412.1961.2022.00066

研究论文

本期目录 | 过刊浏览

高Nb锆合金在含氧蒸汽中耐腐蚀性能恶化的机理

黄建松, 裴文, 徐诗彤, 白勇, 姚美意(

), 胡丽娟, 谢耀平, 周邦新

上海大学材料研究所上海 200072

Degradation Mechanism on Corrosion Resistance of High Nb-Containing Zirconium Alloys in Oxygen-Containing Steam

HUANG Jiansong, PEI Wen, XU Shitong, BAI Yong, YAO Meiyi(

), HU Lijuan, XIE Yaoping, ZHOU Bangxin

Institute of Materials, Shanghai University, Shanghai 200072, China

引用本文:

黄建松, 裴文, 徐诗彤, 白勇, 姚美意, 胡丽娟, 谢耀平, 周邦新. 高Nb锆合金在含氧蒸汽中耐腐蚀性能恶化的机理[J]. 金属学报, 2024, 60(4): 509-521.
Jiansong HUANG, Wen PEI, Shitong XU, Yong BAI, Meiyi YAO, Lijuan HU, Yaoping XIE, Bangxin ZHOU. Degradation Mechanism on Corrosion Resistance of High Nb-Containing Zirconium Alloys in Oxygen-Containing Steam[J]. Acta Metall Sin, 2024, 60(4): 509-521.

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摘要:

为探究高Nb锆合金在含氧蒸汽中耐腐蚀性能恶化的机理，研究了Zr-0.75Sn-0.35Fe-0.15Cr-1.0Nb (质量分数，%)合金在除氧(DE)、300 μg/kg溶解氧(DO)、1000 μg/kg DO的400℃、10.3 MPa过热蒸汽中的腐蚀行为，采用SEM、TEM和XPS分析了氧化膜的显微组织和Nb元素价态。结果表明：Zr-0.75Sn-0.35Fe-0.15Cr-1.0Nb合金在400℃过热蒸汽中的耐腐蚀性能随着DO浓度升高而变差；合金在含氧蒸汽中耐腐蚀性能恶化的机理主要有2方面，一方面是DO加速了氧化膜中Nb元素的氧化，促进了Nb²⁺向Nb⁵⁺的转换；另一方面是DO促进了第二相氧化成m-Nb₂O₅以及非晶，进而促进了裂纹的萌生与生长，裂纹为O的扩散提供了快速通道，氧化膜显微组织的演化速率更快，最终加速了合金的腐蚀进程。

关键词 ：锆合金, 溶解氧, 腐蚀, 显微组织

Abstract：

In some water-cooled nuclear power reactors, a hydrogenation-deoxygenation device is generally not used to simplify the system and save space, which can increase dissolved oxygen (DO) concentration in primary loop water. The increase in DO concentration will inevitably affect the corrosion resistance of zirconium alloy cladding materials. In particular, DO will accelerate the corrosion of Nb-containing zirconium alloys, and the corrosion rate of zirconium alloys with high Nb content is sensitive to DO concentration. In exploring the deterioration mechanism of the corrosion resistance of high-Nb-containing zirconium alloys in oxygen-containing steam, the corrosion behavior of the Zr-0.75Sn-0.35Fe-0.15Cr-1.0Nb (mass fraction, %) alloy was studied in superheated steam through deoxygenation, with 300 μg/kg of DO and 1000 μg/kg of DO at 400^oC and 10.3 MPa. The corrosion behavior was characterized by measuring the mass gain per unit area. SEM was used to observe the fracture morphology of the oxide film; TEM-EDS was used to observe and analyze the morphology, elemental distribution, and crystal structure of the alloy, second-phase particles (SPPs), and oxide film. The elemental distribution on the outer surface of the oxide film was analyzed by XPS, and the valence state of Nb was determined in accordance with the binding energy to analyze the influence of DO on the oxidation behavior of Nb in the oxide film. Results show that the corrosion resistance of the Zr-0.75Sn-0.35Fe-0.15Cr-1.0Nb alloy in superheated steam at 400^oC deteriorates with the increase of DO concentration. The deterioration mechanism of the corrosion resistance of the alloy in oxygen-containing steam is proposed. On the one hand, DO accelerates the oxidation of Nb in the oxide film and promotes the conversion of Nb²⁺ to Nb⁵⁺. On the other hand, DO promotes the oxidation of SPPs to m-Nb₂O₅ (monoclinic) and amorphous phase, thereby promoting the initiation and growth of cracks. These newly generated cracks provide more channels for the diffusion of O^2- and other oxidizing ions to accelerate the oxidation of SPPs near the cracks and the microstructural evolution of the oxide film, thereby accelerating the corrosion of the alloy.

Key words： zirconium alloy dissolved oxygen corrosion microstructure

收稿日期: 2022-02-21

ZTFLH:

TG146.4

基金资助:国家自然科学基金项目(51871141)

通讯作者: 姚美意，yaomeiyi@shu.edu.cn，主要从事核电用锆合金和ATF包壳材料研究

Corresponding author: YAO Meiyi, professor, Tel: (021)56338586, E-mail: yaomeiyi@shu.edu.cn

作者简介: 黄建松，男，1996年生，硕士

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图1 Zr-0.75Sn-0.35Fe-0.15Cr-1.0Nb合金显微组织及第二相选区电子衍射花样和尺寸分布

图2 Zr-0.75Sn-0.35Fe-0.15Cr-1.0Nb合金在400℃、10.3 MPa的除氧(DE)、300 μg/kg溶解氧(DO)和1000 μg/kg DO过热蒸汽中的腐蚀增重曲线和双对数曲线

Environment	Transition		Pre-transition		Post-transition
Environment		$t 0$ / d	$w t 0$ / (mg·dm^-2)	$k 1$ / (mg·dm^-2·d $- n 1$ )	$n 1$	$k 2$ / (mg·dm^-2·d $- n 2$ )	$n 2$
DE	72	57.39	4.78	0.46	1.38	0.86
300 μg·kg^-1 DO	40	48.73	7.58	0.43	1.62	0.88
1000 μg·kg^-1 DO	40	51.84	4.67	0.55	1.73	0.89

表1 合金在400℃、10.3 MPa的DE、300 μg/kg DO和1000 μg/kg DO过热蒸汽中的氧化动力学参数

图3 Zr-0.75Sn-0.35Fe-0.15Cr-1.0Nb合金在400℃、10.3 MPa不同含氧过热蒸汽中腐蚀42 d的氧化膜断口形貌

图4 Zr-0.75Sn-0.35Fe-0.15Cr-1.0Nb合金在400℃、10.3 MPa不同含氧过热蒸汽中腐蚀42 d的氧化膜横截面显微组织TEM明场像

图5 合金在400℃、10.3 MPa的DE过热蒸汽中腐蚀42 d的氧化膜横截面HAADF像及对应元素的EDS面分布图

图6 图5b中所示的SPP1~SPP3第二相的HRTEM像及FFT分析

图7 合金在400℃、10.3 MPa的300 μg/kg DO过热蒸汽中腐蚀42 d氧化膜截面显微组织HAADF像及对应元素的EDS面分布图

图8 图7b和c中所示的SPP1~SPP3第二相的HRTEM像及FFT分析

图9 合金在400℃、10.3 MPa的1000 μg/kg DO过热蒸汽中腐蚀42 d氧化膜截面显微组织HAADF像及对应元素EDS面分布图

图10 图9b和c中所示的SPP1~SPP3第二相HRTEM像及FFT分析

表2 合金在400℃、10.3 MPa不同环境中腐蚀42 d的氧化膜中第二相的氧化产物

图11 Ar+溅射180 s后300 DO/160 d和1000 DO/130 d样品氧化膜表面的Nb元素XPS精细谱及分峰拟合图

表3 300 DO/160 d与1000 DO/130 d样品氧化膜中Nb元素不同价态占比 (atomic fraction / %)

1	Cao Y L, Wang S W, Xiong W B, et al. Features and application analysis of the small modular reactors[J]. Nucl. Electron. Detect. Technol., 2014, 34: 801
1	曹亚丽, 王韶伟, 熊文彬等. 小型模块化反应堆特性及应用分析[J]. 核电子学与探测术, 2014, 34: 801
2	Bradhurst D H, Shirvington P J, Heuer P M. The effects of radiation and oxygen on the aqueous oxidation of zirconium and its alloys at 290^oC[J]. J. Nucl. Mater., 1973, 46: 53 doi: 10.1016/0022-3115(73)90122-0
3	Motta A T, Comstock R J, Count A. Corrosion of zirconium alloys used for nuclear fuel cladding[J]. Annu. Rev. Mater. Res., 2015, 45: 311 doi: 10.1146/matsci.2015.45.issue-1
4	Kumar M K, Aggarwal S, Beniwal D, et al. Localized oxidation of zirconium alloys in high temperature and pressure oxidizing environments of nuclear reactors[J]. Mater. Corros., 2014, 65: 244
5	Cox B. Some thoughts on the mechanisms of in-reactor corrosion of zirconium alloys[J]. J. Nucl. Mater., 2005, 336: 331 doi: 10.1016/j.jnucmat.2004.09.029
6	Jeong Y H, Park S Y, Lee M H, et al. Out-of-pile and in-pile performance of advanced zirconium alloys (HANA) for high burn-up fuel[J]. J. Nucl. Sci. Mater., 2006, 43: 977
7	Zhou B X, Yao M Y, Li Z K, et al. Optimization of N18 zirconium alloy for fuel cladding of water reactors[J]. J. Mater. Sci. Technol., 2012, 28: 606
8	Liu J Z. Structure Nuclear Materials[M]. Beijing: Chemical Industry Press, 2007: 56
8	刘建章. 核结构材料[M]. 北京: 化学工业出版社, 2007: 56
9	Kim Y S, Kim S K, Bang J G, et al. Effects of Sn and Nb on massive hydriding kinetics of Zr ± XSn ± YNb alloy[J]. J. Nucl. Mater., 2000, 279: 335 doi: 10.1016/S0022-3115(99)00281-0
10	Kim H G, Yong H J, Kim T H. Effect of isothermal annealing on the corrosion behavior of Zr-xNb alloys[J]. J. Nucl. Mater., 2004, 326: 125 doi: 10.1016/j.jnucmat.2004.01.015
11	Dai J X, Gong Z M, Xu S T, et al. In situ study on the initial oxidation behavior of zirconium alloys with near-ambient pressure XPS[J]. Acta Phys. Chim. Sin., 2022, 38: 76
11	戴久翔, 龚忠苗, 徐诗彤等. 锆合金初始氧化行为的原位近常压XPS研究[J]. 物理化学学报, 2022, 38: 76
12	Jeong Y H, Kim H G, Kim D J, et al. Influence of Nb content in the α-matrix on the corrosion behavior of Zr-xNb binary alloys[J]. J. Nucl. Mater., 2003, 323: 72 doi: 10.1016/j.jnucmat.2003.08.031
13	Wang B Y, Zhou B X, Wang Z, et al. Corrosion resistance of Zr-0.72Sn-0.32Fe-0.14Cr-xNb alloys in 500^oC superheated steam[J]. Acta. Metall. Sin., 2015, 51: 1545
13	王波阳, 周邦新, 王桢等. Zr-0.72Sn-0.32Fe-0.14Cr-xNb合金在500℃过热蒸汽中的耐腐蚀性能[J]. 金属学报, 2015, 51: 1545 doi: 10.11900/0412.1961.2015.00254
14	Wu Y, Chen B, Lin X D, et al. Corrosion behavior of 90Nb-10Zr alloy in 500^oC superheated steam[J]. Rare. Met. Mater. Eng., 2021, 50: 4437
14	吴悦, 陈兵, 林晓冬等. 90Nb-10Zr合金在500℃过热蒸气中的腐蚀行为[J]. 稀有金属材料与工程, 2021, 50: 4437
15	Yao M Y, Zhou B X. Mechanism of the accelerated corrosion of Zr-Nb alloys in lithiated water from the viewpoint of β-Nb oxidation[J]. J. Shanghai Univ.: Nat. Sci. Ed., 2020, 26: 681
15	姚美意, 周邦新. 从β-Nb氧化角度探究Zr-Nb系锆合金在LiOH水溶液中腐蚀加速的机理[J]. 上海大学学报(自然科学版), 2020, 26: 681 doi: 10.12066/j.issn.1007-2861.2258
16	Xu S T, Huang J S, Pei W, et al. Effect of oxygen content in 400^oC superheated steam on the corrosion resistance of Zr-xSn-0.35Fe-0.15Cr-0.15Nb alloys[J]. Corros. Sci., 2022, 198: 110135 doi: 10.1016/j.corsci.2022.110135
17	Kumar M K, Aggarwal S, Kain V, et al. Effect of dissolved oxygen on oxidation and hydrogen pick up behaviour—Zircaloy vs Zr-Nb alloys[J]. Nucl. Eng. Des., 2010, 240: 985 doi: 10.1016/j.nucengdes.2009.12.021
18	Wei T G, Lin J K, Long C S, et al. Effect of dissolved oxygen in steam on the corrosion behaviors of zirconium alloys[J]. Acta. Metall. Sin., 2016, 52: 209 doi: 10.11900/0412.1961.2015.00219
18	韦天国, 林建康, 龙冲生等. 蒸汽中的溶解氧对锆合金腐蚀行为的影响[J]. 金属学报, 2016, 52: 209 doi: 10.11900/0412.1961.2015.00219
19	Liu Q D, Zhang H, Zeng Q F, et al. Pre-transition corrosion behavior of SZA-4 and ZIRLO alloys in dissolved oxygen aqueous condition at 360^oC[J]. J. Mech. Eng. 2019, 55(8): 88
19	刘庆冬, 张浩, 曾奇锋等. SZA-4和ZIRLO锆合金在360℃含氧水环境中的腐蚀行为[J]. 机械工程学报, 2019, 55(8): 88 doi: 10.3901/JME.2019.08.088
20	Qin W, Nam C, Li H L, et al. Tetragonal phase stability in ZrO₂ film formed on zirconium alloys and its effects on corrosion resistance[J]. Acta Mater., 2007, 55: 1695 doi: 10.1016/j.actamat.2006.10.030
21	Olsson C O A, Landolt D. Atmospheric oxidation of a Nb-Zr alloy studied with XPS[J]. Corros. Sci., 2004, 46: 213 doi: 10.1016/S0010-938X(03)00139-2
22	Hauffe K. Oxidation of Metal.[M]. New York: Plenum Press, 1965: 176
23	Li M S. High Temperature Corrosion of Metal[M]. Beijing: Metallurgical Industry Press, 2001: 55
23	李美栓. 金属的高温腐蚀[M]. 北京: 冶金工业出版社, 2001: 55
24	Li T F. High Temperature Oxidation and Thermal Corrosion in Metals[M]. Beijing: Chemical Industry Press, 2003: 18
24	李铁藩. 金属高温氧化和热腐蚀.[M]. 北京: 化学工业出版社, 2003: 18
25	Cao X X, Yao M Y, Peng J C, et al. Corrosion behavior of Zr(Fe _x, Cr_1- _x)₂ alloys in 400^oC superheated steam[J]. Acta Metall. Sin, 2011, 47: 882
25	曹潇潇, 姚美意, 彭建超等. Zr(Fe _x, Cr_1- _x)₂合金在400℃过热蒸汽中的腐蚀行为[J]. 金属学报, 2011, 47: 882 doi: 10.3724/SP.J.1037.2011.00251
26	Yang W D. Reactor Materials Science.[M]. 2nd Ed., Beijing: Atomic Energy Press, 2006: 123
26	杨文斗. 反应堆材料学[M]. 第二版, 北京: 原子能出版社, 2006: 123
27	Zhou B X, Li Q, Yao M Y, et al. Microstructure of oxide films formed on zircaloy-4[J]. Corros. Prot., 2009, 30: 589
27	周邦新, 李强, 姚美意等. Zr-4合金氧化膜的显微组织研究[J]. 腐蚀与防护, 2009, 30: 589
28	Liu W Q, Li Q, Zhou B X, et al. Effect of heat treatment on the corrosion resistance for new zirconium-based alloy[J]. Nucl. Power Eng., 2005, 26: 249
28	刘文庆, 李强, 周邦新等. 热处理制度对N18新锆合金耐腐蚀性能的影响[J]. 核动力工程, 2005, 26: 249

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