High Temperature Steam Oxidation Behavior of Zr-1Nb- xFe Alloy Under Simulated LOCA Condition

doi:10.11900/0412.1961.2022.00632

Acta Metall Sin

2024, Vol. 60

Issue (5): 670-680 DOI: 10.11900/0412.1961.2022.00632

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High Temperature Steam Oxidation Behavior of Zr-1Nb- xFe Alloy Under Simulated LOCA Condition

WANG Jinxin¹, YAO Meiyi¹(

), LIN Yuchen¹, CHEN Liutao², GAO Changyuan², XU Shitong¹, HU Lijuan¹, XIE Yaoping¹, ZHOU Bangxin¹

1 Institute of Materials, Shanghai University, Shanghai 200072, China
2 China Nuclear Power Technology Research Institute Co. Ltd., Shenzhen 518031, China

Cite this article:

WANG Jinxin, YAO Meiyi, LIN Yuchen, CHEN Liutao, GAO Changyuan, XU Shitong, HU Lijuan, XIE Yaoping, ZHOU Bangxin. High Temperature Steam Oxidation Behavior of Zr-1Nb- xFe Alloy Under Simulated LOCA Condition. Acta Metall Sin, 2024, 60(5): 670-680.

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Abstract

Zirconium alloys are widely used as fuel cladding materials in water-cooled nuclear reactors due to their properties such as small thermal neutron absorption cross section, good corrosion resistance to high-temperature steam and high-pressure water, excellent mechanical properties and good compatibility with UO₂. However, under loss of coolant accident (LOCA) conditions, zirconium alloy undergoes high-temperature steam oxidation and loses its structural integrity, threatening nuclear reactor safety. With the development of the nuclear power industry, increasing demands are put forward for zirconium alloys to withstand higher burnup; hence, studying their behavior under high-temperature steam oxidation during simulated LOCA is crucial. Fe is a significant alloying element in zirconium alloys, and its addition can improve their properties. Zr-1Nb alloy is a commercial alloy with excellent corrosion resistance, and adding an appropriate amount of Fe (0.1%-0.4%; mass fraction) can further enhance the corrosion resistance of the Zr-1Nb alloy under normal operating conditions. However, the effect of adding Fe on the high-temperature steam oxidation behavior of the Zr-1Nb alloy is unclear. Therefore, the oxidation behavior of Zr-1Nb-xFe (x = 0, 0.05, 0.2, and 0.4; mass fraction, %) alloys were investigated in steam at 800, 900, 1000, 1100, and 1200^oC for 3600 s using a simultaneous thermal analyzer with a steam generator. The microstructure and microhardness of the samples before and after oxidation were analyzed using a metallographic microscope and Vickers hardness tester. The results revealed that adding Fe generally reduced the high-temperature steam oxidation resistance of Zr-1Nb-xFe alloys from 800^oC to 1100^oC for 3600 s. The effect of Fe contents on the oxidation behavior of the Zr-1Nb alloy was complex and did not show a consistent change with increasing Fe content. When oxidized at 1200^oC for 3600 s, the difference in Fe content had hardly any effect on the high-temperature steam oxidation resistance of Zr-1Nb-xFe alloys. As the oxidation temperature increased, the oxidation kinetics of the four alloys generally changed from a parabolic to a linear pattern, even occurring to multiple transitions, which was closely related to the change process of the α↔β phase for the zirconium matrix and the monoclinic (m) ↔ tetragonal (t) phase for ZrO₂.

Key words: zirconium alloy loss of coolant accident (LOCA) high-temperature steam oxidation microstructure phase transition

Received: 18 December 2022

ZTFLH:

TL341

Fund: National Natural Science Foundation of China(51871141)

Corresponding Authors: YAO Meiyi, professor, Tel: 13818897458, E-mail: yaomeiyi@shu.edu.cn

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	WANG Jinxin
	YAO Meiyi
	LIN Yuchen
	CHEN Liutao
	GAO Changyuan
	XU Shitong
	HU Lijuan
	XIE Yaoping
	ZHOU Bangxin

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https://www.ams.org.cn/EN/10.11900/0412.1961.2022.00632 OR https://www.ams.org.cn/EN/Y2024/V60/I5/670

Table 1 Chemical compositions of Zr-1Nb-xFe alloys

Fig.1 Oxidation kinetics curves of four alloys oxidized in 800^oC (a), 900^oC (b), 1000^oC (c), 1100^oC (d), and 1200^oC (e) steam for 3600 s

Table 2 Oxidation kinetic parameters of four alloys oxidized in 800-1200^oC steam for 3600 s

Table 3 Compared to 0Fe alloy, the percentages of weight gain change for 0.05Fe, 0.2Fe, and 0.4Fe alloys oxidized in 800-1200^oC steam for 3600 s

Fig.2 Cross-sectional OM images of 0Fe (a1, a2), 0.05Fe (b1, b2), 0.2Fe (c1, c2), and 0.4Fe (d1, d2) alloys oxidized in 800^oC steam for 3600 s (Figs.2a2-d2 are the enlarged images of middle area of Figs.2a1-d1, respectively)

Fig.3 Cross-sectional OM images of 0Fe (a1, a2), 0.05Fe (b1, b2), 0.2Fe (c1, c2), and 0.4Fe (d1, d2) alloys oxidized in 900^oC steam for 3600 s (Figs.3a2-d2 are the enlarged images of middle area of Figs.3a1-d1, respectively)

Fig.4 Cross-sectional OM images of 0Fe (a1-a3), 0.05Fe (b1-b3), 0.2Fe (c1-c3), and 0.4Fe (d1-d3) alloys oxidized in 1000^oC (a1-d1), 1100^oC (a2-d2), and 1200^oC (a3-d3) steam for 3600 s

Fig.5 Layer thickness ratios of four alloys oxidized in 800^oC (a), 900^oC (b), 1000^oC (c), 1100^oC (d), and 1200^oC (e) steam for 3600 s

Table 4 Vickers hardnesses of different tissue layers in cross section of four alloys oxidized in 800-1200^oC steam for 3600 s

1	Jia Y J, Lin X H, Zou X W, et al. Research & development history, status and prospect of zirconium alloys[J]. Mater. China, 2022, 41: 354
	贾豫婕, 林希衡, 邹小伟等. 锆合金的研发历史、现状及发展趋势[J]. 中国材料进展, 2022, 41: 354
2	Liu J Z. Nuclear Structural Materials[M]. Beijing: Chemical Industry Press, 2007: 5
	刘建章. 核结构材料[M]. 北京: 化学工业出版社, 2007: 5
3	Wang R S, Geng J Q, Weng L K, et al. Zirconium alloy cladding be-haviors under LOCA condition[J]. Mater. Rev., 2011, 25(suppl.2) :501
	王荣山, 耿建桥, 翁立奎等. LOCA工况下锆合金包壳的行为概述[J]. 材料导报, 2011, 25(): 501
4	Kim J H, Lee M H, Choi B K, et al. Embrittlement behavior of zircaloy-4 cladding during oxidation and water quench[J]. Nucl. Eng. Des., 2005, 235: 67 doi: 10.1016/j.nucengdes.2004.08.030
5	Gao Y, Yang M X, Hu Y, et al. Effect of cooling rate on residual plasticity of homemade ZIRLO alloy after LOCA[J]. Atomic. Energy Sci. Technol., 2019, 53: 1310
	高阳, 杨明馨, 胡勇等. 冷却速率对国产ZIRLO合金LOCA后残余塑性的影响[J]. 原子能科学技术, 2019, 53: 1310
6	Grosse M, Stuckert J, Steinbrück M, et al. Secondary hydriding during LOCA—Results from the QUENCH-L0 test[J]. J. Nucl. Mater., 2012, 420: 575 doi: 10.1016/j.jnucmat.2011.11.045
7	Shishov V N. The evolution of microstructure and deformation stability in Zr-Nb-(Sn,Fe) alloys under neutron irradiation[J]. J. ASTM Int., 2010, 7: 1
8	Qiu J, Zhao W J, Guilbert T, et al. High temperature oxidation behaviours of three zirconium alloys[J]. Acta. Metall Sin., 2011, 47: 1216 doi: 10.3724/SP.J.1037.2011.00211
	邱军，赵文金， Guilbert T 等. 3种锆合金的高温氧化行为[J]. 金属学报， 2011, 47: 1216
9	Gao W, Zhang X, Wang Z P, et al. Study of oxidation behavior of M5 and ZIRLO zirconium alloy in high temperature vapor[J]. J. Xi'an Technol. Univ., 2016, 36: 473
	高巍, 张娴, 王正品等. M5和ZIRLO合金高温水蒸气氧化行为研究[J]. 西安工业大学学报, 2016, 36: 473
10	Huang W. Conventional corrosion behavior and high temperature steam oxidation behavior under simulated LOCA for Zr-1Nb-xM alloys[D]. Shanghai: Shanghai University, 2020
	黄微. Zr-1Nb-xM合金的常规腐蚀行为及模拟LOCA下的高温蒸汽氧化行为研究[D]. 上海: 上海大学, 2020
11	Baek J H, Park K B, Jeong Y H. Oxidation kinetics of Zircaloy-4 and Zr-1Nb-1Sn-0.1Fe at temperatures of 700-1200^oC[J]. J. Nucl. Mater., 2004, 335: 443 doi: 10.1016/j.jnucmat.2004.08.007
12	Liu Y Z, Qiu J, Liu X, et al. Oxidation kinetics of N18 zirconium alloy at temperatures of 600-1200^oC in steam[J]. Nucl. Power Eng., 2010, 31(2): 85
	刘彦章, 邱军, 刘欣等. N18锆合金在600~1200℃蒸汽中的氧化行为研究[J]. 核动力工程, 2010, 31(2): 85
13	Ma S C, Sun Y Z, Chen W C, et al. Study of fuel cladding-steam reaction under a loss of coolant-accident (LOCA)[J]. Atomic Energy Sci Technol., 1993, 27: 376
	马树春, 孙源珍, 陈望春等. PWR失水事故工况下燃料包壳与水蒸汽反应研究[J]. 原子能科学技术, 1993, 27: 376
14	Zhang J N, Yao M Y, Zha X P, et al. Effect of Nb addition on high temperature steam oxidation behavior of Zr-0.75Sn-0.35Fe-0.15Cr alloy[J]. Rare Met. Mater. Eng., 2022, 51: 1837
	张佳楠, 姚美意, 查学鹏等. 添加Nb对Zr-0.75Sn-0.35Fe-0.15Cr合金高温蒸汽氧化行为的影响[J]. 稀有金属材料与工程, 2022, 51: 1837
15	Qu C. Oxidation behavior of Zr-0.75Sn-0.35Fe-0.15Cr-xNb alloys in high-temperature steam[D]. Shanghai: Shanghai University, 2019
	瞿忱. Zr-0.75Sn-0.35Fe-0.15Cr-xNb合金的高温蒸汽氧化行为研究[D]. 上海: 上海大学, 2019
16	Chabretou V, Hoffmann P B, Trapp-Pritsching S, et al. Ultra low tin quaternary alloys PWR performance-impact of tin content on corrosion resistance, irradiation growth, and mechanical properties[A]. Zirconium in the Nuclear Industry: 16th International Symposium[C]. West Conshohocken: American Society for Testing and Materials, 2011: 1
17	Kim H G, Park J Y, Jeong Y H. Ex-reactor corrosion and oxide characteristics of Zr-Nb-Fe alloys with the Nb/Fe ratio[J]. J. Nucl. Mater., 2005, 345: 1 doi: 10.1016/j.jnucmat.2005.04.061
18	Wang R S, Weng L K, Zhang Y W, et al. Development of research on corrosion resistance of Zr-Nb alloy[J]. Mater. Rep., 2011, 25(13): 10
	王荣山, 翁立奎, 张晏玮等. Zr-Nb合金耐腐蚀性能的研究进展[J]. 材料导报, 2011, 25(13): 105
19	Toffolon-Masclet C, Barbéris P, Brachet J C, et al. Study of Nb and Fe precipitation in α-phase temperature range (400 to 500℃) in Zr-Nb-(Fe-Sn) alloys[A]. Zirconium in the Nuclear Industry: 14th International Symposium[C]. Stockholm, Sweden: American Society for Testing and Materials, 2005: 1
20	Wang R S, Weng L K, Zhang Y W, et al. Effect of Fe on the precipitate characteristics and out-of-pile corrosion behavior of Zr-1Nb-xFe alloys[J]. Mater. Sci. Forum, 2013, 743-744: 1 doi: 10.4028/www.scientific.net/MSF
21	Broy Y, Garzarolli F, Seibold A, et al. Influence of transition elements Fe, Cr, and V on long-time corrosion in PWRs[A]. Zirconium in the Nuclear Industry: 12th International Symposium[C]. West Conshohocken: American Society for Testing and Materials, 2000: 609
22	Garzarolli F, Broy Y, Busch R A. Comparison of the long-time corrosion behavior of certain Zr alloys in PWR, BWR, and laboratory tests[A]. Zirconium in the nuclear industry: 11th International Symposium[C]. West Conshohocken: American Society for Testing and Materials, 1996: 850
23	Li M S. High Temperature Corrosion of Metals[M]. Beijing: Metallurgical Industry Press, 2001: 36
	李美栓. 金属的高温腐蚀[M]. 北京: 冶金工业出版社, 2001: 36
24	Wang D, Zhang Y P, Wu S H, et al. Development of oxidation model for zirconium alloy cladding and application in the analysis of cladding behavior under loss of coolant accident[J]. J. Nucl. Mater., 2022, 561: 153564 doi: 10.1016/j.jnucmat.2022.153564
25	Négyesi M, Burda J, Bláhová O, et al. The influence of hydrogen on oxygen distribution inside Zry-4 fuel cladding[J]. J. Nucl. Mater., 2011, 416: 288 doi: 10.1016/j.jnucmat.2011.06.013
26	Li C B, Song Q, Yang X W, et al. Experimental investigation of the phase relations in the Fe-Zr-Y ternary system[J]. Materials, 2022, 15: 593 doi: 10.3390/ma15020593
27	Chiang T W, Chernatynskiy A, Noordhoek M J, et al. Anisotropy in oxidation of zirconium surfaces from density functional theory calculations[J]. Comput. Mater. Sci., 2015, 98: 112 doi: 10.1016/j.commatsci.2014.10.052
28	Noordhoek M J, Liang T, Chiang T W, et al. Mechanisms of Zr surface corrosion determined via molecular dynamics simulations with charge-optimized many-body (COMB) potentials[J]. J. Nucl. Mater., 2014, 452: 285 doi: 10.1016/j.jnucmat.2014.05.023
29	Hou X M, Chou K C. Investigation of the effects of temperature and oxygen partial pressure on oxidation of zirconium carbide using different kinetics models[J]. J. Alloys. Compd., 2011, 509: 2395 doi: 10.1016/j.jallcom.2010.11.028
30	Nagase F, Otomo T, Uetsuka H. Oxidation kinetics of low-Sn zircaloy-4 at the temperature range from 773 to 1,573 K[J]. J. Nucl. Sci. Technol., 2003, 40: 213 doi: 10.1080/18811248.2003.9715351
31	Yan Y, Garrison B E, Smith T S, et al. Investigation of high-temperature oxidation kinetics and residual ductility of oxidized samples of sponge-based E110 alloy cladding tubes[J]. MRS Adv., 2017, 2: 1203 doi: 10.1557/adv.2016.641
32	Ackermann O R J, Garg S P, Rauh E G. High-temperature phase diagram for the system Zr-O[J]. J. Am. Ceram. Soc., 1977, 60: 341 doi: 10.1111/jace.1977.60.issue-7-8
33	Yao M Y, Luan B F. Zirconium alloys used in water-cooled reactors[A]. Nuclear Reactor Materials[M]. Shanghai: Shanghai Jiao Tong University Press, 2021: 524
	姚美意, 栾佰峰. 水冷核反应堆用锆合金[A]. 核反应堆材料[M].上海: 上海交通大学出版社, 2021: 524
34	Ma M X, Zhu D C, Wang Z X, et al. Effect of Zr addition on microstructure and wear properties of CoCrCuFeMn high-entropy alloy[J]. Adv. Eng. Sci., 2021, 53(6): 204
	马明星, 朱达川, 王志新等. Zr元素对CoCrCuFeMn高熵合金组织及耐磨性能的影响[J]. 工程科学与技术, 2021, 53(6): 204
35	Uetsuka H, Furuta T, Kawasaki S. Embrittlement of Zircaloy-4 due to oxidation in environment of stagnant steam[J]. J. Nucl. Sci. Technol., 1982, 19: 158 doi: 10.1080/18811248.1982.9734128
36	Zha X P. Oxidation behavior and mechanical properties of Zr-0.75Sn-0.35Fe-0.15Cr-xNb alloy under simulated loss of coolant accident conditions[D]. Shanghai: Shanghai University, 2022: 61
	查学鹏. Zr-0.75Sn-0.35Fe-0.15Cr-xNb合金在模拟失水事故下的氧化行为和力学性能研究[D]. 上海: 上海大学, 2022: 61

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