Mn对Hastelloy N合金700℃氧化行为的影响
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摘要
采用增重法,研究了不同Mn含量的Hastelloy N合金在700℃/200 h内下的恒温氧化行为。利用扫描电镜(SEM)、能谱分析仪(EDS)和X射线衍射仪(XRD)分析了不同Mn含量的Hastelloy N合金700℃氧化膜的氧化动力学、形貌、物相组成以及氧化层中元素分布情况。结果表明Hastelloy N合金在700℃氧化动力曲线符合抛物线规律,随着Mn含量的增加氧化增重逐渐减少,氧化膜厚度分别为17.0, 14.8, 12.9, 10.0μm。不同Mn含量的Hastelloy N合金在700℃下的平均氧化速率分别为0.054, 0.050, 0.048, 0.040 g·(m~2·h)~(-1),根据氧化等级评定, 4种合金均属于完全抗氧化等级。氧化层表面皆无明显剥落,氧化膜呈分层现象,其中外层为NiO, Fe_2O_3, NiFe_2O_4等复合氧化物,内层为Cr_2O_3, MoO_2, NiMn_2O_4等氧化物。Mn的添加使氧化膜外层与基体之间生成NiMn_2O_4尖晶石层,阻碍了O元素向内扩散以及金属元素的向外扩散,有效提高了Hastelloy N合金的抗氧化性能。
The isothermal oxidation behavior of Hastelloy N alloy with different Mn contents in air at 700 ℃ for 200 h was investigated by mass gain method. Oxidation kinetics, morphology and component of the oxide scale formed on Hastelloy N alloy were analyzed by means of scanning electron microscopy(SEM), energy dispersive spectrometer(EDS) and X-ray diffraction(XRD). The results showed that the oxidation kinetic curves of Hastelloy N alloy followed parabolic law at 700 ℃, the oxidation weight gain decreased with the increase of Mn content and the thickness of the oxide film was 17.0, 14.8, 12.9 and 10.0 μm, respectively. The oxidation rates of Hastelloy N alloy with different Mn contents at 700 ℃ were 0.054, 0.050, 0.048 and 0.040 g·(m~2·h)~(-1), respectively. The alloys were estimated to be completely antioxidant according to the oxidation rate. The surface of oxidation film was no significant spallation, and the oxide film was layered. The outer oxide film of Hastelloy N superalloy mainly consisted of NiO, Fe_2O_3 and other oxide composites, the middle layer consisted of Cr_2O_3, MoO_2, NiMn_2O_4 and other oxides. The addition of Mn could lead to the formation of NiMn_2O_4 spinel layer between the outer layer of oxide film and the substrate, which hindered the inward diffusion of O and the outward diffusion of metal elements, effectively improving the oxidation resistance of Hastelloy N alloy at 700 ℃.
The isothermal oxidation behavior of Hastelloy N alloy with different Mn contents in air at 700 ℃ for 200 h was investigated by mass gain method. Oxidation kinetics, morphology and component of the oxide scale formed on Hastelloy N alloy were analyzed by means of scanning electron microscopy(SEM), energy dispersive spectrometer(EDS) and X-ray diffraction(XRD). The results showed that the oxidation kinetic curves of Hastelloy N alloy followed parabolic law at 700 ℃, the oxidation weight gain decreased with the increase of Mn content and the thickness of the oxide film was 17.0, 14.8, 12.9 and 10.0 μm, respectively. The oxidation rates of Hastelloy N alloy with different Mn contents at 700 ℃ were 0.054, 0.050, 0.048 and 0.040 g·(m~2·h)~(-1), respectively. The alloys were estimated to be completely antioxidant according to the oxidation rate. The surface of oxidation film was no significant spallation, and the oxide film was layered. The outer oxide film of Hastelloy N superalloy mainly consisted of NiO, Fe_2O_3 and other oxide composites, the middle layer consisted of Cr_2O_3, MoO_2, NiMn_2O_4 and other oxides. The addition of Mn could lead to the formation of NiMn_2O_4 spinel layer between the outer layer of oxide film and the substrate, which hindered the inward diffusion of O and the outward diffusion of metal elements, effectively improving the oxidation resistance of Hastelloy N alloy at 700 ℃.
引文
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[3] Liu Y H, Yang C, Wang X J, Li H L, Lu Y L, Zhou X T. Coating technique on structural materials of molten salt reactor [J]. Chinese Journal of Rare Metals, 2016, 40(9): 908.(刘艳红, 杨超, 王晓婧, 李怀林, 陆燕玲, 周兴泰. 熔盐堆结构材料的涂层技术研究 [J]. 稀有金属, 2016, 40(9): 908.)
[4] Fan J X, Lu Y L, Li Z J, Dong J S, Zhang J X, Zhou X T, Huai P. Iso-thermal oxidation behavior of GH3535 superalloy at 700 ℃ [J]. Rare Metal Materials and Engineering, 2015, 44(8): 1953.(范金鑫, 陆燕玲, 李志军, 董加胜, 张继祥, 周兴泰, 怀平. GH3535合金700 ℃恒温氧化行为研究 [J]. 稀有金属材料与工程, 2015, 44(8): 1953.)
[5] Kvackaj T, Zrnik J, Vrchovinsky V, Wangyao P. Controlled rolling of Hastelloy-N [J]. High Temperature Materials and Processes, 2002, 21(6): 351.
[6] Liu J X, Zhang J X, Lu Y L, Li X K, Li Z J, Zhou X T. Effect of long-term aging on microstructure and mechanical properties of alloy C276 [J]. Acta Metallurgica Sinica, 2013, 49(6): 763.(刘锦溪, 张继祥, 陆燕玲, 李肖科, 李志军, 周兴泰. 长期时效对C276合金组织和力学性能的影响 [J]. 金属学报, 2013, 49(6): 763)
[7] Jiang M H, Xu H J, Dai Z M. Advanced fission energy program-TMSR nuclear energy system [J]. Bulletin of the Chinese Academy of Sciences, 2012, 27(3): 366.(江绵恒, 徐洪杰, 戴志敏. 未来先进核裂变能—TMSR核能系统 [J]. 中国科学院院刊, 2012, 27(3): 366.)
[8] Rosenthal M W, Briggs R B, Hauhenreieh P N. The development, status of molten-salt reactor [R]. ORNL-4812, Tennessee: Oak Ridge National Laboratory, 1972.
[9] Koger J W. Evaluation of Hastelloy N alloys after nine years exposure to both a molten fluoride salt and air at temperatures from 700 to 560 ℃ [R]. ORNL-TM-4189, Tennessee: Oak Ridge National Laboratory, 1972.
[10] Roche T K. The influence of composition upon the 1500 °F creep-rupture strength and microstructure of molybdenum-chromium-iron-nickel base alloys [R]. ORNL-2524, Tennessee: Oak Ridge National Laboratory, 1958.
[11] Guo J T. Materials Science and Engineering for Superalloys [M]. Beijing: Science Press, 2008. 583.(郭建亭. 高温合金材料学(中) [M]. 北京: 科学出版社, 2008. 583.)
[12] Tang S Q, Qu S J, Feng A H, Feng C, Cui K B, Shen J. Recent advances in high temperature oxidation resistance of TiAl based alloys [J]. Chinese Journal of Rare Metals, 2017, 41(1): 81.(汤守巧, 曲寿江, 冯艾寒, 冯聪, 崔扣彪, 沈军. TiAl基合金高温抗氧化研究进展 [J]. 稀有金属, 2017, 41(1): 81.)
[13] Veronica Miguel-Pérez, Ana Martínez-Amesti, María Luisa Nó, Aitor Larranga, María Isabel Arriortua. Oxide scale formation on different metallic interconnects for solid oxide fuel cells [J]. Corrosion Science, 2012, 60(6): 38.
[14] Gordon R Holcomb, David E Alman. The effect of manganese additions on the active evaporation of chromium in Ni-Cr alloys [J]. Scripta Materialia, 2006, 54(10): 1821.
[15] Yun D W, Seo S M, Jeong H W, Yoo Y S. The effects of the minor alloying elements Al, Si and Mn on the cyclic oxidation of Ni-Cr-W-Mo alloys [J]. Corrosion Science, 2014, 83(6): 176.
[16] Li T F. High Temperature and Hot Oxidation Corrosion of Metals [M]. Beijing: Chemical Industry Press, 2003. 183.(李铁藩. 金属高温氧化和热腐蚀 [M]. 北京: 化学工业出版社, 2003. 183.)