Effect of Sn on Initial Corrosion Behavior of Zirconium Alloy in 280 ℃ LiOH Aqueous Solution

doi:10.11900/0412.1961.2019.00170

Acta Metall Sin

2019, Vol. 55

Issue (12): 1551-1560 DOI: 10.11900/0412.1961.2019.00170

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Effect of Sn on Initial Corrosion Behavior of Zirconium Alloy in 280 ℃ LiOH Aqueous Solution

YAO Meiyi^1,²(

),LIN Yuchen^1,²,HOU Keke^1,²,LIANG Xue^1,²,HU Pengfei^1,²,ZHANG Jinlong^1,²,ZHOU Bangxin^1,²

1. Institute of Materials, Shanghai University, Shanghai 200072, China
2. Laboratory for Microstructures, Shanghai University, Shanghai 200444, China

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YAO Meiyi, LIN Yuchen, HOU Keke, LIANG Xue, HU Pengfei, ZHANG Jinlong, ZHOU Bangxin. Effect of Sn on Initial Corrosion Behavior of Zirconium Alloy in 280 ℃ LiOH Aqueous Solution. Acta Metall Sin, 2019, 55(12): 1551-1560.

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Abstract

Zirconium alloys are widely used as fuel cladding and core structure materials for water-cooled nuclear reactors due to its low thermal neutron absorption cross section, good corrosion resistance, moderate mechanical properties and good compatibility with UO₂. Corrosion is one of the main factors affecting the service life of zirconium alloy cladding. The influence of initial corrosion behavior of zirconium alloys and the crystal structure of the oxide film formed at the early stage on the microstructural evolution of the oxide film at the later stage has gradually attracted people's attention. Sn is an important alloying element in zirconium alloys. In order to study the effect of Sn on the initial corrosion behavior of zirconium alloys, coarse-grain TEM thin samples of Zr-0.75Sn-0.35Fe-0.15Cr and Zr-1.5Sn-0.35Fe-0.15Cr (mass fraction, %) zirconium alloys were corroded in 280 ℃, 6.3 MPa and 0.01 mol/L LiOH aqueous solution for short period. In order to ensure the observation of the crystal structure evolution process under the same thickness and grain orientation, the cross-section thin section samples were cut by focused ion beam (FIB), and then the surface and cross-section microstructures of the corroded samples were observed by TEM. Based on the difference in oxygen content caused by the different thickness of the sample around the hole in TEM sample, the effect of Sn on the initial corrosion behavior of zirconium alloy was investigated, as well as the nucleation and growth process of early oxide film. Results showed that the lattice of α-Zr evolved with the increase of oxygen content in the sample from the beginning of oxidation to the formation of ZrO₂. The evolution of the oxide layer on the grain oriented [0001] underwent sub-oxide layer, lattice distortion layer and m-ZrO₂ layer. Compared with Zr-0.75Sn-0.35Fe-0.15Cr alloy, Zr-1.5Sn-0.35Fe-0.15Cr alloy had a thicker oxide layer in the thin section, a lower proportion of lattice distortion layer and a higher proportion of the m-ZrO₂ layer. This illustrates that increasing the Sn content promotes the initial corrosion process of zirconium alloys.

Key words: zirconium alloy initial corrosion crystal structure

Received: 30 May 2019

ZTFLH:

TL341

Fund: National Natural Science Foundation of China(Nos.51871141);National Natural Science Foundation of China(51471102)

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	YAO Meiyi
	LIN Yuchen
	HOU Keke
	LIANG Xue
	HU Pengfei
	ZHANG Jinlong
	ZHOU Bangxin

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https://www.ams.org.cn/EN/10.11900/0412.1961.2019.00170 OR https://www.ams.org.cn/EN/Y2019/V55/I12/1551

Fig.1 TEM images (a~f) and corresponding SAED patterns (a1~f1) of 1# alloy (Zr-0.75Sn-0.35Fe-0.15Cr) large-grain TEM thin sample after short-time corrosion in 280 ℃, 6.3 MPa and 0.01 mol/L LiOH aqueous solution (Figs.1a~f are taken every 500 nm from thick to thin along the diameter of the hole)

Table 1 Zr and O contents and Zr/O atomic ratios in Figs.1a~f

Fig.2 TEM images (a~f) and corresponding SAED patterns (a1~f1) of 11# alloy (Zr-1.5Sn-0.35Fe-0.15Cr) large-grain TEM thin sample after short-time corrosion in 280 ℃, 6.3 MPa and 0.01 mol/L LiOH aqueous solution (Figs.2a~f are taken every 500 nm from thick to thin along the diameter of the hole)

Table 2 Zr and O contents and Zr/O atomic ratios in Figs.2a~f

Fig.3 Cross-sectional microstructure of 1# alloy large-grain TEM thin sample after short-time corrosion in 280 ℃, 6.3 MPa and 0.01 mol/L LiOH aqueous solution(a) TEM image (Inset is the magnification of area B1)(b) HRTEM image of area B1 in Fig.3a (The sample thickness is about 300 nm)(c~f) FFT graphs and analysis results corresponding to the areas C~F in Fig.3b, respectively

Fig.4 Cross-sectional microstructures of 1# alloy large-grain TEM thin sample after short-time corrosion in 280 ℃, 6.3 MPa and 0.01 mol/L LiOH aqueous solution(a) TEM image (Inset is the magnification of area B2)(b) HRTEM image of area B2 in Fig.4a (The sample thickness is about 200 nm)(c~f) FFT graphs and analysis results corresponding to the areas C~F in Fig.4b, respectively

Fig.5 Cross-sectional microstructures of 11# alloy large-grain TEM thin sample after short-time corrosion in 280 ℃, 6.3 MPa and 0.01 mol/L LiOH aqueous solution(a) TEM image (Inset is the magnification of area B1)(b) HRTEM image of area B1 in Fig.5a (The sample thickness is about 300 nm)(c~f) FFT graphs and analysis results corresponding to the areas C~F in Fig.5b, respectively

Fig.6 Cross-sectional microstructures of 11# alloy large-grain TEM thin sample after short-time corrosion in 280 ℃, 6.3 MPa and 0.01 mol/L LiOH aqueous solution(a) TEM image (Inset is the magnification of area B2)(b) HRTEM image of area B2 in Fig.6a (The sample thickness is about 200 nm)(c~f) FFT graphs and analysis results corresponding to the areas C~F in Fig.6b, respectively

Table 3 TEM thin sample cross-section oxidation process, proportion of lattice distortion layer, proportion of m-ZrO₂ and thickness of oxide layer in short-time corrosion of 280 ℃, 6.3 MPa and 0.01 mol/L LiOH aqueous solution, where the oxide layer thickness and proportion of each layer are taken from the sample thickness of 300 nm

Fig.7 Corrosion gain curves of two alloys with fine grains in 360 ℃, 18.6 MPa and 0.01 mol/L LiOH aqueous solution (a), and of two alloys with large grains in 280 ℃, 6.3 MPa and 0.01 mol/L aqueous solution (b)

[1]	Yang W D. Reactor Materials Science [M]. 2nd Ed., Beijing: Atomic Energy Press, 2006: 260
[1]	(杨文斗. 反应堆材料学 [M]. 第2版. 北京: 原子能出版社, 2006: 260)
[2]	Liu J Z. Nuclear Structure Materials [M]. Beijing: Chemical Industry Press, 2007: 41
[2]	(刘建章. 核结构材料 [M]. 北京: 化学工业出版社, 2007: 41)
[3]	Chen H M, Ma C L, Bai X D. Corrosion and Protection of Nuclear Reactor Materials [M]. Beijing: Atomic Energy Press, 1984: 188
[3]	(陈鹤鸣, 马春来, 白新德. 核反应堆材料腐蚀及其防护 [M]. 北京: 原子能出版社, 1984: 188)
[4]	Harada M, Kimpara M, Abe K. Effect of alloying elements on uniform corrosion resistance of zirconium-based alloys in 360 ℃ water and 400 ℃ steam [A]. Zirconium in the Nuclear Industry: Ninth International Symposium [C]. Conshohocken, Philadelphia: American Society for Testing and Materials, 1991: 368
[5]	Graham R A, Eucken C M. Controlled composition zircaloy-2 uniform corrosion resistance [A]. Zirconium in the Nuclear Industry: Ninth International Symposium [C]. Conshohocken, Philadelphia: American Society for Testing and Materials, 1991: 279
[6]	Garde A M, Pati S R, Krammen M A, et al. Corrosion behavior of zircaloy-4 cladding with varying tin content in high-temperature pressurized water reactors [A]. Zirconium in the Nuclear Industry: Tenth International Symposium [C]. Conshohocken, Philadelphia: American Society for Testing and Materials, 1994: 760
[7]	Eucken C M, Finden P T, Trapp-Pritsching S, et al. Influence of chemical composition on uniform corrosion of zirconium-base alloys in autoclave tests [A]. Zirconium in the Nuclear Industry: Eighth International Symposium [C]. Conshohocken, Philadelphia: American Society for Testing and Materials, 1989: 113
[8]	Yueh H K, Kesterson R L, Comstock R J, et al. Improved ZIRLOTM cladding performance through chemistry and process modifications [A]. Zirconium in the Nuclear Industry: 14th International Symposium [C]. Conshohocken, Philadelphia: American Society for Testing and Materials, 2005: 330
[9]	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
[10]	Takeda K, Anada H. Mechanism of corrosion rate degradation due to tin [A]. Zirconium in the Nuclear Industry: Twelfth International Symposium [C]. Conshohocken, Philadelphia: American Society for Testing and Materials, 2000: 592
[11]	Zhou B X, Li Q, Yao M Y, et al. Microstructure of oxide films formed on zircaloy-4 [J]. Corros. Prot., 2009, 30: 589
[11]	(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)
[12]	Zhou B X, Li Q, Yao M Y, et al. Microstructure evolution of oxide films formed on zircaloy-4 during autoclave tests [J]. Nucl. Power Eng., 2005, 26: 364
[12]	(周邦新, 李强, 姚美意等. 锆-4合金在高压釜中腐蚀时氧化膜显微组织的演化 [J]. 核动力工程, 2005, 26: 364)
[13]	Zhou B X, Li Q, Yao M Y, et al. Effect of water chemistry and composition on microstructural evolution of oxide on Zr alloys [J]. J. ASTM Int., 2008, 5(2): 101121
[14]	Zhou B X, Li Q, Liu W Q, et al. The effects of water chemistry and composition on the microstructure evolution of oxide films on zirconium alloys during autoclave tests [J]. Rare Met. Mater. Eng., 2006, 35: 1009
[14]	(周邦新, 李强, 刘文庆等. 水化学及合金成分对锆合金腐蚀时氧化膜显微组织演化的影响 [J]. 稀有金属材料与工程, 2006, 35: 1009)
[15]	Li S L, Yao M Y, Zhang X, et al. Effect of adding Cu on the corrosion resistance of M5 alloy in super-heated steam at 500 ℃ [J]. Acta Metall. Sin., 2011, 47: 163
[15]	(李士炉, 姚美意, 张欣等. 添加Cu对M5合金在500 ℃过热蒸汽中耐腐蚀性能的影响 [J]. 金属学报, 2011, 47: 163)
[16]	Zhu L, Yao M Y, Sun G C, et al. Effect of Bi addition on the corrosion resistance of Zr-1Nb alloy in deionized water at 360 ℃ and 18.6 MPa [J]. Acta Metall. Sin., 2013, 49: 51
[16]	(朱莉, 姚美意, 孙国成等. 添加Bi对Zr-1Nb合金在360 ℃和18.6 MPa去离子水中耐腐蚀性能的影响 [J]. 金属学报, 2013, 49: 51)
[17]	Ploc R A. Transmission electron microscopy of α-ZrO2 films formed in 573 K oxygen [J]. J. Nucl. Mater., 1976, 61: 79
[18]	Warr B D, Elmoselhi M B, Newcomb S B, et al. Oxide characteristics and their relationship to hydrogen uptake in zirconium alloys [A]. Zirconium in the Nuclear Industry: Ninth International Symposium [C]. Conshohocken, Philadelphia: American Society for Testing and Materials, 1991: 740
[19]	Gou S Q, Zhou B X, Chen C M, et al. Investigation of oxide layers formed on zircaloy-4 coarse-grained specimens corroded at 360 ℃ in lithiated aqueous solution [J]. Corros. Sci, 2015, 92: 237
[20]	Ni N, Hudson D, Wei J, et al. How the crystallography and nanoscale chemistry of the metal/oxide interface develops during the aqueous oxidation of zirconium cladding alloys [J]. Acta Mater., 2012, 60: 7132
[21]	Hu J, Garner A, Ni N, et al. Identifying suboxide grains at the metal-oxide interface of a corroded Zr-1.0%Nb alloy using (S) TEM, transmission-EBSD and EELS [J]. Micron, 2015, 69: 35
[22]	Foord D T, Newcomb S B. The formation of ω-Zr during the oxidation of zircaloy-4 [A]. Proceedings of the 52nd Meeting of the Electron Microscopy Society of America [C]. New Orleans: AIP Publishing, 1994: 668
[23]	Foord D T, Newcomb S B. The microstructural characterisation of factors which determine the degradation behaviour of zircaloy-4 [A]. Proceedings of the Third International Conference on the Microscopy of Oxidation [C]. Cambridge, U.K.World Scientific Publishing, 1996: 488
[24]	Bossis P, Lelièvre G, Barberis P, et al. Multi-scale characterization of the metal-oxide interface of zirconium alloys [A]. Zirconium in the Nuclear Industry: 12th International Symposium [C]. Conshohocken, Philadelphia: American Society for Testing and Materials, 2000: 918
[25]	Wang Z. TEM study on the behavior of zirconium alloy in the early stage of oxidation in different environments [D]. Shanghai: Shanghai University, 2016
[25]	(王祯. TEM研究锆合金在不同环境下氧化初期的行为 [D]. 上海: 上海大学, 2016)
[26]	Du C X. Study on the microstructure of early oxide film of Zr-4 alloy corrosion [D]. Shanghai: Shanghai University, 2011
[26]	(杜晨曦. Zr-4合金腐蚀早期氧化膜的显微组织研究 [D]. 上海: 上海大学, 2011)
[27]	Xie S J. A Study of the mechanism for the anisotropic corrosion of zirconium alloys [D]. Shanghai: Shanghai University, 2017
[27]	(谢世敬. 锆合金腐蚀各向异性的机理研究 [D]. 上海: 上海大学, 2017)

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