Zr-0.7Sn-0.35Nb-0.3Fe-xGe合金在高温高压LiOH 水溶液中耐腐蚀性能的研究
收稿日期: 2012-07-19
修回日期: 2012-09-18
网络出版日期: 2012-12-11
基金资助
国家自然科学基金项目50971084和国家先进压水堆重大专项2011ZX06004-023资助
STUDY ON THE CORROSION RESISTANCE OF Zr–0.7Sn–0.35Nb–0.3Fe–xGe ALLOY IN LITHIATEDWATER AT HIGH TEMPERATURE UNDER HIGH PRESSURE
Received date: 2012-07-19
Revised date: 2012-09-18
Online published: 2012-12-11
Supported by
Supported by National Natural Science Foundation of China (No.50971084) and National Advanced Pressurized Water Reactor Project of China (No.2011ZX06004–023)
利用静态高压釜腐蚀实验研究了Zr-0.7Sn-0.35Nb-0.3Fe-xGe (x=0.05, 0.1, 0.2, 质量分数, %)系列合金在360 ℃/18.6 MPa/0.01 mol/L LiOH水溶液中的耐腐蚀性能; 利用TEM和SEM分别观察了合金基体的显微组织和氧化膜的显微组织. 结果表明: Ge可以显著改善Zr-0.7Sn-0.35Nb-0.3Fe金在高温高压LiOH水溶液中的耐腐蚀性能, 当Ge含量为0.1\%时, 合金的耐腐蚀性能最佳. 在Zr-0.7Sn-0.35Nb-0.3Fe-xGe系列合金中发现尺寸较小的hcp结构的Zr(Fe, Cr, Nb)2型、Zr(Fe, Cr, Nb, Ge)2型第二相和尺寸较大的四方结构的Zr3Ge型第二相. 腐蚀220 d的Zr-0.7Sn-0.35Nb-0.3Fe-0.1Ge合金氧化膜致密,厚度较薄, 几乎没有微孔隙和微裂纹, ZrO2柱状晶较多. 这说明添加适量的Ge不仅可以有效延缓氧化膜中空位扩散凝聚形成微孔隙和微孔隙发展形成微裂纹的过程, 还可以延迟ZrO2由柱状晶向等轴晶的演化, 从而改善合金的耐腐蚀性能.
谢兴飞 张金龙 朱莉 姚美意 周邦新 彭剑超 . Zr-0.7Sn-0.35Nb-0.3Fe-xGe合金在高温高压LiOH 水溶液中耐腐蚀性能的研究[J]. 金属学报, 2012 , 48(12) : 1487 -1494 . DOI: 10.3724/SP.J.1037.2012.00434
The corrosion resistance of Zr–0.7Sn–0.35Nb–0.3Fe–xGe (x=0.05, 0.1, 0.2, mass fraction, %) alloys was investigated in lithiated water with 0.01 mol/L LiOH at 360 /18.6 MPa by autoclave tests. The microstructures of the alloys and oxide films on the corroded specimens were observed by TEM and SEM. The results show that the corrosion resistance of the Zr–0.7Sn–0.35Nb–0.3Fe alloys in lithiated water at high temperature under high pressure is markedly improved by Ge addition. The alloy with 0.1%Ge shows the best corrosion resistance. In Zr–0.7Sn–0.35Nb–0.3Fe–xGe alloys, there exists fine Zr(Fe, Cr, Nb)2 and Zr(Fe, Cr, Nb, Ge)2 second phase particles (SPPs) with a close–packed hexagonal crystal structure (hcp) and coarse Zr3Ge SPPs with a tetragonal crystal structure (TET). The oxide films formed on the Zr–0.7Sn–0.35Nb–0.3Fe–0.1Ge alloys corroded for 220 d are compact and thin. The micro–pores and micro–cracks are hardly detected and many ZrO2 columnar grains exist in the oxide films formed on the Zr–0.7Sn–0.35Nb–0.3Fe–0.1Ge alloys. This indicates that the suitable amount of Ge could not only delay the process that the vacancies diffuse to form micro–pores and micro–pores develop to form micro–cracks, but also could retard the evolution from ZrO2 columnar grains to ZrO2 equiaxed grains.
Key words： zirconium alloy; Ge; corrosion resistance; microstructure; oxide film
[1] Liu J Z. Structure Nuclear Materials. Beijing: Chemical Industry Press, 2007: 19
(刘建章. 核结构材料. 北京: 化学工业出版社, 2007: 19)
[2] Zhao W J, Zhou B X, Miao Z, Peng Q, Jiang Y R, Jiang H M, Pang H. Atom Energ Sci Technol, 2005; 39(suppl):1
(赵文金, 周邦新, 苗志, 彭倩, 蒋有荣, 蒋宏曼, 庞华. 原子能科学技术, 2005; 39(增刊): 1)
[3] Nikulina A V, Markelov V A. In: Bradley E R, Sabol G P eds., Zirconium in the Nuclear Industry: 11th International Symposium, ASTM STP 1295, Garmisch
Partenkirchen Germany: ASTM International, 1996: 785
[4] Sabol G P, Comstock R J. In: Garde A M, Bradley E R eds., Zirconium in the Nuclear Industry: 10th International Symposium, ASTM STP 1245, Baltimore, MD:
ASTM International, 1994: 724
[5] Jung Y I, Lee M H, Kim H G, Park J Y, Jeong Y H. J Alloys Compd, 2009; 479: 423
[6] Yang W D. Reactor Materials Science. 2nd Ed., Beijing: Atomic Energy Press, 2006: 260
(杨文斗. 反应堆材料学. 第二版, 北京: 原子能出版社, 2006: 260)
[7] Liu W Q, Zhu X Y, Wang X J, Li Q, Yao M Y, Zhou B X. Atom Energ Sci Technol, 2010; 44: 1477
(刘文庆, 朱晓勇, 王晓娇, 李强, 姚美意, 周邦新. 原子能科学技术, 2010; 44: 1477)
[8] Kim J M, Jeong Y H, Kim I S. J Nucl Mater, 2000; 280: 235
[9] Liu W Q, Li Q, Zhou B X, Yao M Y. Nucl Power Eng, 2003; 24(1): 33
(刘文庆, 李强, 周邦新, 姚美意. 核动力工程, 2003; 24(1): 33)
[10] Wang J K. Modern Ge Metallurgy. Beijing: Metallurgy Industry Press, 2005: 58
(王吉坤. 现代锗冶金. 北京: 冶金工业出版社, 2005: 58)
[11] Zhou B X, Li Q, Yao M Y, Liu W Q, Chu Y L. In: Kammenzind B, Limback M eds., Zirconium in the Nuclear Industry: 15th International Symposium, ASTM STP 1505,
West Conshohochen: American Society for Testing and Materials, 2009: 360
[12] Schaffer M, Schaffer B, Ramasse Q. Ultramicroscopy, 2012; 114: 62
[13] Zhou B X, Yao M Y, Li Q, Xia S, Liu W Q, Chu Y L. Rare Met Mater Eng, 2007; 36: 1317
(周邦新, 姚美意, 李强, 夏爽, 刘文庆, 褚于良. 稀有金属材料与工程, 2007; 36: 1317)
[14] Charquet D, Hahn R, Ortlib E. In: Van Swam L F P, Eucken C M eds., Zircorium in the Nuclear Industry: 8th International Symposium, ASTM STP 1023, Philadelphia:
ASTM International, 1989: 405
[15] Anada H, Takeda K. In: Sabol G P, Bradley E R eds., Zircorium in the Nuclear Industry: 11th International Symposium, ASTM STP 1295, Ann Arbor: ASTM International,
1996: 35
[16] Wadman B, Lai Z, Andren H O, Nystrom A L, Rudling P, Pettersson H. In: Garde A M, Bradley E R eds., Zirconium in the Nuclear Industry: 10th International Symposium
ASTM STP 1245, Ann Arbor: ASTM International, 1994: 579
[17] Zhou B X, Peng J C, Yao M Y, Li Q, Xia S, Du C X, Xu G. In: Limback M, Barb´eris P eds., Zirconium in the Nuclear Industry: 16th International Symposium, ASTM
STP 1529, Bridgeport: ASTM International, 2011: 620
[18] Zhang X, Yao M Y, Li S L, Zhou B X. Acta Metall Sin, 2011; 47: 1112
(张欣, 姚美意, 李士炉, 周邦新. 金属学报, 2011; 47: 1112)
[19] Zhou B X, Li Q, Liu W Q, Yao M Y, Chu Y L. Rare Met Mater Eng, 2006; 35: 1009
(周邦新, 李强, 刘文庆, 姚美意, 褚于良. 稀有金属材料与工程, 2006; 35: 1009)
[20] Zhou B X, Li Q, Yao M Y, Liu W Q, Chu Y L. Corros Prot, 2009; 30: 589
(周邦新, 李强, 姚美意, 刘文庆, 褚于良. 腐蚀与防护, 2009; 30: 589)
[21] Li T F. Metal High Temperature Oxidation and Thermal Corrosion. Beijing: Chemical Industry Press, 2003: 51
(李铁藩. 金属高温氧化和热处理. 北京: 化学工业出版社, 2003: 51)
[22] Yang X L, Zhou B X, Jiang Y R, Li C. Nucl Power Eng, 1994; 15(1): 79
(杨晓林, 周邦新, 蒋有荣, 李聪. 核动力工程, 1994; 15(1): 79)
[23] Toffolon–Masclet C, Brachet J C, Jago G. J Nucl Mater, 2002; 305: 224
[24] Cao X X, Yao M Y, Peng J C, Zhou B X. Acta Metall Sin, 2011; 47: 882
(曹潇潇, 姚美意, 彭剑超, 周邦新. 金属学报, 2011; 47: 882)
[25] Yilmazbayhan A, Breval E. J Nucl Mater, 2006; 349: 265
/
| 〈 |
|
〉 |
