Corrosion Behavior of Second Phase Alloys of β-(Nb, Zr) in Deionized Water at 360 ℃

doi:10.11900/0412.1961.2016.00389

Acta Metall Sin

2017, Vol. 53

Issue (4): 447-454 DOI: 10.11900/0412.1961.2016.00389

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Corrosion Behavior of Second Phase Alloys of β-(Nb, Zr) in Deionized Water at 360 ℃

Bing CHEN^1,²,Changyuan GAO^1,²,Jiao HUANG^1,²,Yajing MAO^1,²,Meiyi YAO^1,²(

),Jinlong ZHANG^1,²,Bangxin ZHOU^1,²,Qiang LI^1,²

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

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Bing CHEN,Changyuan GAO,Jiao HUANG,Yajing MAO,Meiyi YAO,Jinlong ZHANG,Bangxin ZHOU,Qiang LI. Corrosion Behavior of Second Phase Alloys of β-(Nb, Zr) in Deionized Water at 360 ℃. Acta Metall Sin, 2017, 53(4): 447-454.

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Abstract

Zirconium alloys are widely used as fuel cladding materials in water-cooled nuclear power reactors due to their low thermal neutron cross-section, good mechanical properties and corrosion resistance. The waterside corrosion is one of main factors that influence the service life of zirconium alloys. The corrosion of zirconium alloys occurs at the oxide/metal (O/M) interface, so the characteristics of the oxide film do have an impact on the oxidation process of zirconium alloys, which are affected by the oxidation behavior of second phase particles (SPPs) in zirconium alloys. E110 (Zr-1Nb, mass fraction, %) and M5 (Zr-1Nb-0.16O) alloys are Zr-Nb series alloys used in commercial presently. The major SPPs in Zr-Nb series alloys are bcc β-Nb. β-Nb SPPs in zirconium alloys are very fine, and it is inconvenient to analyze their oxidation processes due to the effect of α-Zr matrix. Therefore, based on the composition and crystal structure of β-Nb, two kinds of β-(Nb, Zr) SPPs alloys, 90Nb-10Zr and 50Nb-50Zr alloys were prepared by vacuum non-consumable arc smelting, and were corroded in autoclave with deionized water at 360 ℃ and 18.6 MPa for 11 d. XRD was used to analyze the crystal structure and phase composition of β-(Nb, Zr) specimens before and after oxidation. SEM and TEM equipped with EDS were used to investigate the microstructures of the external surface and the cross-section of oxide layers. Results show that the 90Nb-10Zr and 50Nb-50Zr alloys are oxidized into amorphous and crystalline oxides. The crystalline oxide formed on 90Nb-10Zr alloy is monoclinic Nb₂O₅, but the crystalline oxide formed on 50Nb-50Zr alloy is tetragonal (Zr, Nb)O₂.

Key words: zirconium alloy β-(NbZr) alloy corrosion

Received: 26 August 2016

Fund: Supported by National Natural Science Foundation of China (No.51471102) and National Advanced Pressurized Water Reactor Project of China (No.2011ZX06004-023)

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	Bing CHEN
	Changyuan GAO
	Jiao HUANG
	Yajing MAO
	Meiyi YAO
	Jinlong ZHANG
	Bangxin ZHOU
	Qiang LI

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https://www.ams.org.cn/EN/10.11900/0412.1961.2016.00389 OR https://www.ams.org.cn/EN/Y2017/V53/I4/447

Fig.1 XRD spectra of the 90Nb-10Zr (a) and 50Nb-50Zr (b) alloys before corrosion

Fig.2 Microstructures of the as-cast 90Nb-10Zr (a) and 50Nb-50Zr (b) alloys

Fig.3 SEM images of the external surface of oxide films on 90Nb-10Zr (a) and 50Nb-50Zr (b) alloys corroded in deionized water at 360 ℃, 18.6 MPa for 11 d

Fig.4 XRD spectra of 90Nb-10Zr (a) and 50Nb-50Zr(b) alloys corroded in deionized water at 360 ℃, 18.6 MPa for 11 d

Fig.5 TEM image of the cross-sectional oxide film on 90Nb-10Zr alloy corroded in deionized water at 360 ℃, 18.6 MPa for 11 d (Areas A and C are shown according to different contrast and morphology from the surrounding area, and area B is the observation area of Fig.6)

Fig.6 Magnified TEM (a) and HRTEM (b) images of the oxide film on 90Nb-10Zr alloy in deionized water at 360 ℃, 18.6 MPa for 11 d(a) magnified TEM image of area B in Fig.5 (Insets show SAED patterns of position 1 with monoclin- ic structure Nb₂O₅ and position 2 with amorphous structure)(b) HRTEM image of position 3 in Fig.6a (Inset shows FFT image of square area with monoclinic structure Nb₂O₅)

Fig.7 Analyses of the needle-like oxide on 90Nb-10Zr alloy corroded in deionized water at 360 ℃, 18.6 MPa for 11 d(a) TEM image of the needle-like oxide(b) SAED pattern of position 4 with monoclin- ic structure Nb₂O₅ in Fig.7a(c) EDS of position 4 in Fig.7a

Fig.8 HAADF image of the oxide film on 50Nb-50Zr alloy corroded in deionized water at 360 ℃, 18.6 MPa for 11 d (HAADF—high-angle annular dark field)

Table 1 EDS results of positions 1, 2 and 3 in Fig.6a(atomic fraction / %)

Fig.9 TEM image and corresponding SAED patterns (insets) (a), and EDS results of seven positions in Fig.9a (b) of the oxide film on the 50Nb-50Zr alloy corroded in deionized water at 360 ℃, 18.6 MPa for 11 d

Fig.10 HRTEM and corresponding FFT images of positions 2 (a), 3 (b) and 6 (c) at the layer 1 of oxide film on 50Nb-50Zr alloy in Fig.9a

[1]	Zhou W J, Zhou B X, Miao Z, et al.Development of Chinese advanced zirconium alloys[J]. At. Energy Sci. Technol., 2005, 39(Suppl.): 2
[1]	(赵文金, 周邦新, 苗志等. 我国高性能锆合金的发展[J]. 原子能科学技术, 2005, 39(增刊): 2)
[2]	Bojinov M, Karastoyanov V, Kinnunen P, et al.Influence of water chemistry on the corrosion mechanism of a zirconium-niobium alloy in simulated light water reactor coolant conditions[J]. Corros. Sci., 2010, 52: 54
[3]	Nikulina A V, Markelov V A, Peregud M M.Zirconium alloy E635 as a material for fuel rod cladding and other components of VVER and RBMK cores [A]. Zirconium in the Nuclear Industry: Eleventh International Symposium, ASTM STP 1295[C]. West Conshohocken, Philadelphia: American Society for Testing and Materials, 1996: 785
[4]	Müller S, Lanzani L.Corrosion of zirconium alloys in concentrated lithium hydroxide solutions[J]. J. Nucl. Mater., 2013, 439: 251
[5]	Anada H, Takeda K.Microstructure of oxides on zircaloy-4, 1.0 Nb zircaloy-4, and zircaloy-2 formed in 10.3-MPa steam at 673 K [A]. Zirconium in the Nuclear Industry: Eleventh International Symposium, ASTM STP 1295[C]. West Conshohocken, Philadelphia: American Society for Testing and Materials, 1996: 35
[6]	Perkins R A, Busch R A.Corrosion of zircaloy in the presence of LiOH [A]. Zirconium in the Nuclear Industry: Ninth International Symposium, ASTM STP 1132[C]. Philadelphia: American Society for Testing and Materials, 1991: 595
[7]	Shebaldov P V, Peregud M M, Nikulina A V, et al.E110 alloy cladding tube properties and their interrelation with alloy structure-phase condition and impurity content [A]. Zirconium in the Nuclear Industry: Twelfth International Symposium, ASTM STP 1354[C]. Philadelphia: American Society for Testing and Materials, 2000: 545
[8]	Sun F T, Yao M Y, Xu L, et al.Effect of adding dilute Si on corrosion resistance of zirconium alloys[J]. J. Shanghai Univ.(Nat. Sci.), 2015, 21: 182
[8]	(孙风涛, 姚美意, 徐龙等. 添加微量Si对锆合金耐腐蚀性能的影响[J]. 上海大学学报(自然科学版), 2015, 21: 182)
[9]	Kim H G, Choi B K, Park J Y, et al.Analysis of oxidation behavior of the β-Nb phase formed in Zr-1.5Nb alloy by using the HVEM[J]. J. Alloys Compd., 2009, 481: 867
[10]	Yang W D.Reactor Materials Science [M]. Beijing: Atomic Energy Press, 2000: 19
[10]	(杨文斗. 反应堆材料学 [M]. 北京: 原子能出版社, 2000: 19)
[11]	Sabol G P, Comstock R J, Nayak U P.Effect of dilute alloy additions of molybdenum, niobium, and vanadium on zirconium corrosion [A]. Zirconium in the Nuclear Industry: Twelfth International Symposium, ASTM STP 1354[C]. Philadelphia: American Society for Testing and Materials, 2000: 525
[12]	Li Q, Liang X, Peng J C, et al.Oxidation behavior of the β-Nb phase precipitated in Zr-2.5Nb alloy[J]. Acta Metall. Sin., 2011, 47: 893
[12]	(李强, 梁雪, 彭剑超等. Zr-2.5Nb合金中β-Nb相的氧化过程[J]. 金属学报, 2011, 47: 893)
[13]	Gong W J, Zhang H L, Wu C F, et al.The role of alloying elements in the initiation of nanoscale porosity in oxide films formed on zirconium alloys[J]. Corros. Sci., 2013, 77: 391
[14]	Proff C, Abolhassani S, Lemaignan C.Oxidation behaviour of binary zirconium alloys containing intermetallic precipitates[J]. J. Nucl. Mater., 2011, 416: 125
[15]	Proff C, Abolhassani S, Lemaignan C.Oxidation behaviour of zirconium alloys and their precipitates——A mechanistic study[J]. J. Nucl. Mater., 2013, 432: 222
[16]	Pêcheur D, Lefebvre F, Motta A T, et al.Precipitate evolution in the zircaloy-4 oxide layer[J]. J. Nucl. Mater., 1992, 189: 318
[17]	Pêcheur D.Oxidation of β-Nb and Zr(Fe, V)2 precipitates in oxide films formed on advanced Zr-based alloys[J]. J. Nucl. Mater., 2000, 278: 195
[18]	Yilmazbayhan A, Breval E, Motta A T, et al.Transmission electron microscopy examination of oxide layers formed on Zr alloys[J]. J. Nucl. Mater., 2006, 349: 265
[19]	Yao M Y, Gao C Y, Huang J, et al.Oxidation behavior of β-Nb precipitates in Zr-1Nb-0.2Bi alloy corroded in lithiated water at 360 ℃[J]. Corros. Sci., 2015, 100: 169
[20]	Cao X X.Study on the corrosion behavior of the second phase particles in zirconium alloy [D]. Shanghai: Shanghai University, 2010
[20]	(曹潇潇. 锆合金中第二相腐蚀行为研究 [D]. 上海: 上海大学, 2010)
[21]	Huang J, Yao M Y, Gao C Y, et al.Analysis of the oxidized surface of 90Nb-10Zr alloy after exposure to lithiated water with 0.01 M LiOH at 360 ℃/18.6 MPa[J]. Corros. Sci., 2016, 104: 269
[22]	Shen Y F.Effect of β-quenching and annealing treatments on the corrosion resistance of zircaloy-4 [D]. Shanghai: Shanghai University, 2012
[22]	(沈月锋. β相水淬及退火处理对Zr-4合金耐腐蚀性能的影响 [D]. 上海: 上海大学, 2012)
[23]	Liang P Y, Dupin N, Fries S G, et al.Thermodynamic assessment of the Zr-O binary system[J]. Z. Metallk., 2001, 92: 747
[24]	Pérez R J, Massih A R.Thermodynamic evaluation of the Nb-O-Zr system[J]. J. Nucl. Mater., 2007, 360: 242
[25]	Ondik H M, McMurdie H F. Phase Diagrams for Zirconium and Zirconia Systems[M]. Ohio: The American Ceramic Society, 1998: 145
[26]	Cambridge U O.The Interactive Ellingham Diagram, Dissemination of IT for the Promotion of Materials Science,

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