对Zr-A和Zr-B锆合金在700-1200 ℃的O2中进行了等温氧化实验, 观察了合金的氧化动力学行为和基体微观结构演变, 并与低Sn的Zr-4合金作了对比. 结果表明, 700-1200 ℃氧化时, 3种锆合金的动力学曲线基本服从抛物线规律, Zr-B合金在700 ℃氧化1200 s后速率出现转折; 800 ℃时Zr-A和Zr-B 合金的氧化速率出现转折; 1000 ℃时3种合金动力学曲线由抛物线变为近似直线; 1100 ℃以上氧化时, 动力学曲线呈抛物线规律, 未出现转折. 在1100 ℃以上氧化时, 合金成分对3种合金的高温氧化性能影响甚微. 依据氧化增重数据得到了3种合金在700-1200 ℃氧化反应的抛物线速率常数Kp的表达式.
Isothermal oxidation behaviors of Zr-alloys Zr-A and Zr-B cladding tubes in flowing oxygen were measured and compared to Zr-4 cladding tube over a wide temperature range from 700 ℃ to 1200 ℃. The results show that the kinetics oxidation curves of all the alloys basically obey the parabolic rate law at the temperature range from 700 ℃ to 1200 ℃. In 700 ℃ oxidation of alloy Zr-B, a rate transition occurrs at about 1200 s. The rate transitions in 800 ℃ curves of alloys Zr-A and Zr-B occurr at about 600 s. The oxidation kinetics curves are changed for all the alloys at 1000 ℃, which is resulted from the crack in the oxide layer due to the ZrO2 phase transformation from a monoclinic structure to a tetragonal structure. At the temperature above 1100 ℃, the oxidation kinetics curves of all the alloys obey the parabolic rate law, and no kinetics changes were observed. The results also show that the alloy composition has a negligible effect on the oxidation resistance at the temperature above 1100 ℃. The parabolic rate constant Kp of the oxidation reaction was get through calculating weight gain due to oxidation.
[1] Baker L, Just L C. ANL–6548, AEC Research and Development Report, Argonne National Laboratory, 1962
[2] Pawel K E, Cathcart J V, Mckee R A. Electrochem Sci Techol, 1979; 126: 1105
[3] Leistikow S, Schanze G. Nucl Eng Des, 1987; 103: 65
[4] Nagase F. Otomo T, Uetsuka H. Nucl Sci Technol, 2003; 40: 213
[5] Sabol G P, Comstock R J, Weiner R, Larouere A P, Stanutz R N. In: Bradly E R, Sabol G P eds., Zirconium in the Nuclear Industry Tenth International Symposiu. ASTM STP 1245, Philadelphia: ASTM International, 1994: 724
[6] Etoh Y, Shimada S, Yasuda T, Ikeda T, Adamson R B, Chen J F, Ishii Y, Takai K. In: Paul D B, Davidson R R eds., Zirconium in the Nuclear Industry Nineth International Symposium, ASTM STP 1129, West Conshohocken, PA: ASTM International, 1992,: 825
[7] Choo K N, Kim Y S. J Nucl Mater, 2001; 297: 5247
[8] Kim J M, Jeong Y H. J Nucl Mater, 1999; 275: 74
[9] Billone M, Yan C, Burtseva Y, Chung H M. In: Fuketa T ed., Summary of Fuel Safety Research Meeting 2005, Tokyo: Japan Atomic Energy Agency, 2006: 168
[10] Asmolov V, Yegorova L, Lioutov K, Konoveyev A, Smirnov V, Goryachev A, Chesanov V, Prokhorov V. In: Monteleone S, Nesmith S eds., Proceeding of the 2002 Nuclear
Safety Research Conference, Washingdon D. C.: Nuclear Regulation Commission, 2003: 109
[11] Baek J H, Park K B, Jeong Y H. J Nucl Mater, 2004; 335: 443
[12] Zhao W J. Rare Met Lett, 2004; 23(5): 15
(赵文金. 稀有金属快报, 2004; 23(5): 15)
[13] Li C, Zhou B X, Zhao W J, Li P, Peng Q, Ying S H, Shen B L. J Nucl Mater, 2002; 304: 134
[14] Peng J H, Li W F, Bechade J L, Maury R. Chin J Rare Met, 2008; 32(1): 1
(彭继华, 李文芳, Bechade J L, Maury R. 稀有金属, 2008; 32(1): 1)
[15] Xue X Y, Bai X D, Tan Z Y, Zhou Q S, Liu J Z. Rare Met Mater Eng, 2004; 33(9): 902
(薛祥义, 白新德, 田振业, 周青山, 刘建章. 稀有金属材料与工程, 2004; 33(9): 902)
[16] American Society for Metals, Metals Handbook Vol.8. 8th Ed., Materials Park: ASM International, 1971: 327
