<i>β</i>-(Nb, Zr)第二相合金在360 ℃去离子水中的腐蚀行为

doi:10.11900/0412.1961.2016.00389

金属学报

2017, Vol. 53

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

本期目录 | 过刊浏览

β-(Nb, Zr)第二相合金在360 ℃去离子水中的腐蚀行为

陈兵^1,²,高长源^1,²,黄娇^1,²,毛亚婧^1,²,姚美意^1,²(

),张金龙^1,²,周邦新^1,²,李强^1,²

1 上海大学材料研究所上海 200072
2 上海大学微结构重点实验室上海200444

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

引用本文:

陈兵,高长源,黄娇,毛亚婧,姚美意,张金龙,周邦新,李强. β-(Nb, Zr)第二相合金在360 ℃去离子水中的腐蚀行为[J]. 金属学报, 2017, 53(4): 447-454.
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 ℃[J]. Acta Metall Sin, 2017, 53(4): 447-454.

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摘要:

为了研究锆合金中β-Nb第二相粒子的腐蚀行为,利用真空非自耗电弧炉熔炼了2种β-(Nb, Zr)第二相合金,分别为90Nb-10Zr合金和50Nb-50Zr合金,在静态高压釜中进行360 ℃、18.6 MPa、去离子水的腐蚀实验,利用带EDS的SEM和TEM分析腐蚀生成氧化膜的显微组织。结果表明：90Nb-10Zr合金与50Nb-50Zr合金的氧化产物都为非晶氧化物与晶态氧化物,其中90Nb-10Zr合金腐蚀生成的晶态氧化物为单斜结构的Nb₂O₅,而50Nb-50Zr合金腐蚀生成的晶态氧化物为四方结构的(Zr, Nb)O₂。

关键词 ：锆合金, β-(NbZr)合金, 腐蚀

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

收稿日期: 2016-08-26

基金资助:国家自然科学基金项目No.51471102和国家先进压水堆重大专项项目No.2011ZX06004-023

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图1 90Nb-10Zr合金和50Nb-50Zr合金腐蚀前的XRD谱

图2 铸态90Nb-10Zr和50Nb-50Zr合金的显微组织

图3 90Nb-10Zr和50Nb-50Zr合金在360 ℃、18.6 MPa、去离子水中腐蚀11 d时的氧化膜外表面SEM像

图4 90Nb-10Zr和50Nb-50Zr合金在360 ℃、18.6 MPa、去离子水中腐蚀11 d时的XRD谱

图5 90Nb-10Zr合金在360 ℃、18.6 MPa、去离子水中腐蚀11 d时的氧化膜TEM像

图6 90Nb-10Zr合金在360 ℃、18.6 MPa、去离子水中腐蚀11 d时的氧化膜TEM像、SAED图及HRTEM像和FFT得到的晶体结构信息

图7 90Nb-10Zr合金在360 ℃、18.6 MPa、去离子水中腐蚀11 d时的针状氧化物的TEM像、SAED图和EDS谱

图8 50Nb-50Zr合金在360 ℃、18.6 MPa、去离子水中腐蚀11 d时的氧化膜HAADF像

表1 图6a中3个位置的EDS结果

图9 50Nb-50Zr合金在360 ℃、18.6 MPa、去离子水中腐蚀11 d时的氧化膜TEM像、SAED图和EDS结果

图10 50Nb-50Zr合金氧化膜layer 1中的位置2、3和6 (图9a)的HRTEM像和FFT结果

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