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金属学报  2015, Vol. 51 Issue (12): 1545-1552    DOI: 10.11900/0412.1961.2015.00254
  本期目录 | 过刊浏览 |
Zr-0.72Sn-0.32Fe-0.14Cr-xNb合金在500 ℃过热蒸汽中的耐腐蚀性能*
王波阳1,周邦新1,2(),王桢1,黄娇1,姚美意1,2,周军3
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
3 西部新锆核材料科技有限公司, 西安 710016
CORROSION RESISTANCE OF Zr-0.72Sn-0.32Fe- 0.14Cr-xNb ALLOYS IN 500 ℃ SUPERHEATED STEAM
Boyang WANG1,Bangxin ZHOU1,2(),Zhen WANG1,Jiao HUANG1,Meiyi YAO1,2,Jun ZHOU3
1 Institute of Materials, Shanghai University, Shanghai 200072
2 Laboratory for Microstructures, Shanghai University, Shanghai 200444
3 Western Energy Material Technologies Co. Ltd., Xi'an 710016
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摘要: 

选用织构相同的Zr-0.72Sn-0.32Fe-0.14Cr-xNb (x=0, 0.12, 0.28, 0.48, 0.97, 质量分数, %)合金片状样品, 利用高压釜在500 ℃, 10.3 MPa过热蒸汽中进行500 h的腐蚀实验, 用TEM和SEM分别观察了合金的显微组织和氧化膜断口形貌, 研究了Nb含量对锆合金耐腐蚀性能的影响. 结果表明, 5种合金样品都未出现疖状腐蚀, 并且各自的轧面(SN面)、垂直于轧向的截面(SR面)和垂直于横向的截面(ST面)上氧化膜的厚度没有明显差异, 没有腐蚀各向异性的特征. 当Nb含量超过0.28%后, 腐蚀250 h后合金的腐蚀速率随着Nb含量的增加而增加, 合金的耐腐蚀性能变差. Nb的添加会对合金中第二相的晶体结构产生影响, 低Nb的合金中主要含fcc结构的Zr(Fe, Cr)2或Zr(Fe, Cr, Nb)2型第二相, 而高Nb的合金中主要含hcp结构的Zr(Fe, Cr, Nb)2型第二相.

关键词 锆合金Nb第二相耐腐蚀性能    
Abstract

Zirconium alloys with low alloying content are mainly used in the nuclear industry as structural materials because of their superior properties in terms of thermal neutron transparency, mechanical strength and corrosion resistance. They are used for fuel cladding tubes and channels. The reaction between zirconium and water at high temperature forms oxide film on the surfaces. In order to further improve the corrosion resistance of Zr-based cladding tubes, research has continued on developing new zirconium alloys. The corrosion resistance of Zr-0.72Sn-0.32Fe-0.14Cr-xNb alloys (x=0, 0.12, 0.28, 0.48, 0.97, mass fraction, %) was investigated in a superheated steam at 500 ℃ and 10.3 MPa by autoclave tests. All the plate specimens of zirconium alloys with thickness of 2.8 mm have a similar texture. The microstructure of alloys and oxide films on the corroded specimens were observed by TEM and SEM. The results showed that no nodular corrosion appeared on these alloys for 500 h exposure. The thickness of oxide layers developed on the rolling surface (SN), the surface perpendicular to the rolling direction (SR) and the surface perpendicular to the transversal direction (ST) after 500 h exposure was close to each other. There was no anisotropic corrosion resistance for these alloys. The corrosion rate of the alloys increased with the increase of Nb content after 250 h exposure when the Nb content exceeded 0.28%. In the alloy with low Nb content, the fcc-Zr(Fe, Cr)2 or fcc-Zr(Fe, Cr, Nb)2 precipitate was mainly formed, while the hcp-Zr(Fe, Cr, Nb)2 precipitate was frequently observed in the alloy with high Nb content. The corrosion resistance of Zr-0.72Sn-0.32Fe-0.14Cr-xNb alloys was improved by decreasing the Nb/Fe ratio. From a point of view for the improving corrosion resistance, the addition of Nb no more than 0.3% is recommended.

Key wordszirconium alloy    Nb    second phase    corrosion resistance
    
基金资助:*国家自然科学基金资助项目51471102

引用本文:

王波阳,周邦新,王桢,黄娇,姚美意,周军. 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(12): 1545-1552.
Boyang WANG, Bangxin ZHOU, Zhen WANG, Jiao HUANG, Meiyi YAO, Jun ZHOU. CORROSION RESISTANCE OF Zr-0.72Sn-0.32Fe- 0.14Cr-xNb ALLOYS IN 500 ℃ SUPERHEATED STEAM. Acta Metall Sin, 2015, 51(12): 1545-1552.

链接本文:

https://www.ams.org.cn/CN/10.11900/0412.1961.2015.00254      或      https://www.ams.org.cn/CN/Y2015/V51/I12/1545

图1  0.97Nb合金经580 ℃退火5 h后的(0001)极图和其轧面法向(ND)、 横向(TD)及轧向(RD)的反极图
Specimen fN fR fT
0Nb 0.765 0.059 0.176
0.12Nb 0.658 0.078 0.264
0.28Nb 0.703 0.083 0.213
0.48Nb 0.727 0.053 0.220
0.97Nb 0.701 0.061 0.238
表1  Zr-0.72Sn-0.32Fe-0.14Cr-xNb合金沿ND, RD和TD的织构因子fN, fR和fT
图2  Zr-0.72Sn-0.32Fe-0.14Cr-xNb合金的TEM像
图3  Zr-0.72Sn-0.32Fe-0.14Cr-xNb合金中第二相形貌及SAED谱
图4  Zr-0.72Sn-0.32Fe-0.14Cr-xNb合金在500 ℃, 10.3 MPa过热蒸汽中腐蚀后的增重曲线
图5  Zr-0.72Sn-0.32Fe-0.14Cr-xNb合金腐蚀250~500 h时平均腐蚀速率随Nb含量的变化
图6  Zr-0.72Sn-0.32Fe-0.14Cr-xNb在500 ℃, 10.3 MPa过热蒸汽中腐蚀500 h后SN面(轧面)上氧化膜的断口形貌
图7  Zr-0.72Sn-0.32Fe-0.14Cr-xNb合金在500 ℃, 10.3 MPa过热蒸汽腐蚀时轧面(SN面)、垂直于轧向的截面(SR面)和垂直于横向的截面(ST面)上氧化膜厚度随腐蚀时间的变化
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