Please wait a minute...
金属学报  2020, Vol. 56 Issue (3): 321-332    DOI: 10.11900/0412.1961.2019.00276
  研究论文 本期目录 | 过刊浏览 |
NbFe22Cr5Al3Mo合金显微组织和耐腐蚀性能的影响
钱月1,孙蓉蓉1,张文怀1,姚美意1(),张金龙1,周邦新1,仇云龙2,杨健3,成国光4,董建新5
1. 上海大学材料研究所 上海 200072
2. 中兴能源装备有限公司 海门 226126
3. 上海大学材料科学与工程学院省部共建高品质特殊钢冶金与制备国家重点实验室 上海 200444
4. 北京科技大学钢铁冶金新技术国家重点实验室 北京 100083
5. 北京科技大学材料科学与工程学院 北京 100083
Effect of Nb on Microstructure and Corrosion Resistance of Fe22Cr5Al3Mo Alloy
QIAN Yue1,SUN Rongrong1,ZHANG Wenhuai1,YAO Meiyi1(),ZHANG Jinlong1,ZHOU Bangxin1,QIU Yunlong2,YANG Jian3,CHENG Guoguang4,DONG Jianxin5
1. Institute of Materials, Shanghai University, Shanghai 200072, China
2. Zhongxing Energy Equipment Co. , Ltd. , Haimen 226126, China
3. State Key Laboratory of Advanced Special Steel, School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China
4. State Key Laboratory of Advanced Metallurgy, University of Science and Technology Beijing, Beijing 100083, China
5. School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China
全文: PDF(30332 KB)   HTML
摘要: 

采用静态高压釜腐蚀实验研究了添加不同含量的Nb (0.5%、1.0%、2.0%,质量分数) 对Fe22Cr5Al3Mo合金在500 ℃、10.3 MPa过热蒸汽中耐腐蚀性能的影响;采用EBSD、TEM、EDS、SEM等手段研究了合金的显微组织及腐蚀不同时间后的氧化膜显微组织。结果表明,添加Nb的合金中析出了Nb(C, N)、Fe2(Nb, Mo)和Cr2(Nb, Mo)第二相,细化了合金晶粒;当Nb≥1.0%时,随着Nb含量的增加,合金的耐腐蚀性能得到进一步改善。合金氧化膜从外向内依次是Fe、Cr、Al的氧化物;含1.0%Nb的合金不同氧化物的界面比不含Nb合金的更清晰,由不同成分氧化物引起的分层现象更明显;含1.0%Nb合金的氧化膜厚度比不含Nb合金的更均匀;在金属和氧化膜界面处,不含Nb合金中的Al氧化膜呈不连续分布,在基体和Cr氧化层中都发现了Al氧化物颗粒,说明不含Nb合金发生了Al的内氧化现象;而1.0%Nb合金中的Al氧化膜呈连续均匀分布,说明添加Nb能够抑制Al的内氧化,促进均匀且致密的Al氧化膜的形成,从而降低合金的氧化速率。

关键词 Fe-Cr-Al合金Nb显微组织腐蚀氧化膜    
Abstract

Fe-Cr-Al alloy is a promising candidate accident tolerant fuel (ATF) cladding material. It is helpful to developing Fe-Cr-Al alloy with excellent corrosion resistance by investigating the effect of chemical composition on its corrosion behavior under the normal condition of simulated nuclear reactor operation. In this work, the effect of Nb content (0.5%, 1.0%, 2.0%, mass fraction) on the corrosion resistance of Fe22Cr5Al3Mo alloys in 500 ℃ and 10.3 MPa superheated steam was investigated by static autoclave tests. The microstructures of the alloys and oxide films formed on the alloys after different exposure time were observed and analyzed by EBSD, TEM, EDS and SEM. The results showed that the second phase particles (SPPs) of Nb(C, N), Fe2(Nb, Mo) and Cr2(Nb, Mo) were precipitated and the grains were finer in the Nb-containing alloys. The corrosion resistance of the alloys was further improved with the increase of Nb content (in the case of Nb≥1.0%). The oxides of Fe, Cr and Al were formed separately in the oxide layer from outside to inside. Compared with the Nb-free alloy, the interfaces of different oxides were clearer and had a more obvious stratification resulting from the oxides with different composition appeared in the oxide film on the alloy with 1.0%Nb. The thickness of oxide film on the alloy with 1.0%Nb was more uniform than that on the alloy without Nb. At the oxide film and metal matrix interface, the alumina layer on the Nb-free alloy was dispersive, and the alumina particles were detected in both the matrix and chromium oxide scale, which illustrated the internal oxidation of aluminum occurred. While the alumina layer on the alloy with 1.0%Nb was more uniform and continuous. This indicated that the addition of Nb inhibited the internal oxidation of aluminum, and promoted the formation of uniform and continuous alumina layer, therefore reduced the oxidation rate of the alloy.

Key wordsFe-Cr-Al alloy    Nb    microstructure    corrosion    oxide film
收稿日期: 2019-08-19     
ZTFLH:  TG142.1  
基金资助:国家自然科学基金项目(51871141)
通讯作者: 姚美意     E-mail: yaomeiyi@shu.edu.cn
Corresponding author: Meiyi YAO     E-mail: yaomeiyi@shu.edu.cn
作者简介: 钱 月,女,1992年生,硕士生

引用本文:

钱月,孙蓉蓉,张文怀,姚美意,张金龙,周邦新,仇云龙,杨健,成国光,董建新. NbFe22Cr5Al3Mo合金显微组织和耐腐蚀性能的影响[J]. 金属学报, 2020, 56(3): 321-332.
Yue QIAN, Rongrong SUN, Wenhuai ZHANG, Meiyi YAO, Jinlong ZHANG, Bangxin ZHOU, Yunlong QIU, Jian YANG, Guoguang CHENG, Jianxin DONG. Effect of Nb on Microstructure and Corrosion Resistance of Fe22Cr5Al3Mo Alloy. Acta Metall Sin, 2020, 56(3): 321-332.

链接本文:

https://www.ams.org.cn/CN/10.11900/0412.1961.2019.00276      或      https://www.ams.org.cn/CN/Y2020/V56/I3/321

AlloyCrAlMoNbCNFe
0Nb22.905.253.640.030.0320.0089Bal.
0.5Nb22.455.173.520.470.0250.0047Bal.
1.0Nb22.895.293.730.980.0220.0039Bal.
2.0Nb23.395.373.841.960.0360.0082Bal.
表1  Fe22Cr5Al3Mo-xNb合金的成分 (mass fraction / %)
图1  Fe22Cr5Al3Mo-xNb合金的XRD谱
图2  Fe22Cr5Al3Mo-xNb合金晶粒晶界的EBSD像
Alloy(110)(200)(211)ā / nm
θ / (°)d / nmθ / (°)d / nmθ / (°)d / nm
0Nb44.480.2035264.790.1437782.190.117190.28747
0.5Nb44.450.2036564.790.1437782.130.117250.28758
1.0Nb44.450.2036564.580.1441982.130.117250.28786
2.0Nb44.240.2045664.310.1447381.410.118110.28935
表2  Fe22Cr5Al3Mo-xNb合金的XRD特征峰参数(θ,d)和晶格常数平均值(ā)
图3  Fe22Cr5Al3Mo-xNb合金中典型第二相粒子的TEM明场像、SAED花样和EDS结果
Alloyhcp-Fe2Nbhcp-Cr2Nbfcc-Cr23C6o-Fe3Cfcc-Nb(C, N)
0Nb--500~800200-
0.5Nb150~200About 500--About 190
1.0Nb150~800500~750--About 185
2.0Nb300~2000500~800--About 170
表3  Fe22Cr5Al3Mo-xNb合金中几种典型第二相尺寸统计 (nm)
图4  Fe22Cr5Al3Mo-xNb合金在500 ℃、10.3 MPa过热蒸汽中的腐蚀增重曲线和腐蚀增重与Nb含量的关系
图5  0Nb和1.0Nb合金在500 ℃、10.3 MPa过热蒸汽中腐蚀不同时间氧化膜外表面SEM像
图6  0Nb和1.0Nb合金在500 ℃、10.3 MPa过热蒸汽中腐蚀不同时间后氧化膜横截面的HAADF像(图6b中三角位置是氧化膜局部破裂区域)
图7  0Nb合金在500 ℃、10.3 MPa过热蒸汽中腐蚀3 h的氧化膜横截面显微组织和成分分析结果
图8  1.0Nb合金在500 ℃、10.3 MPa过热蒸汽中腐蚀3 h的氧化膜横截面显微组织和成分分析结果
图9  0Nb合金在500 ℃、10.3 MPa过热蒸汽中腐蚀500 h的氧化膜横截面显微组织和成分分析结果
图10  1.0Nb合金在500 ℃、10.3 MPa过热蒸汽中腐蚀500 h的氧化膜横截面显微组织和成分分析结果
[1] Zinkle S J, Terrani K A, Gehin J C, et al. Accident tolerant fuels for LWRs: A perspective [J]. J. Nucl. Mater., 2014, 448: 374
[2] Ott L J, Robb K R, Wang D. Preliminary assessment of accident-tolerant fuels on LWR performance during normal operation and under DB and BDB accident conditions [J]. J. Nucl. Mater., 2014, 448: 520
[3] Terrani K A, Zinkle S J, Snead L L. Advanced oxidation-resistant iron-based alloys for LWR fuel cladding [J]. J. Nucl. Mater. , 2014, 448: 420
[4] Goldner F. Development strategy for advanced LWR fuels with enhanced accident tolerance [R]. Germantown: U.S. Department of Energy, 2012
[5] Ni D Y, Li M C, Wu W B, et al. Neutron penalty and advantage analysis of candidate accident-tolerant cladding materials in PWRs [J]. Nucl. Power Eng., 2015, 36(S2): 14
[5] 倪东洋, 李满仓, 吴文斌等. 压水堆候选耐事故包壳材料的中子经济性分析 [J]. 核动力工程, 2015, 36(S2): 14
[6] Chu R. Studies on high-temperature oxidation and its influence mechanism of Fe-Cr-Al alloy [D]. Shenyang: Shenyang Normal University, 2013
[6] 褚 冉. Fe-Cr-Al合金高温氧化及影响机理研究 [D]. 沈阳: 沈阳师范大学, 2013
[7] Quadakkers W J, Naumenko D, Wessel E, et al. Growth rates of alumina scales on Fe-Cr-Al alloys [J]. Oxid. Met., 2004, 61:17
[8] Bo J, Roger B, Jonas M, et al. High temperature properties of a new powder metallurgical FeCrAl alloy [J]. Mater. Sci. Forum, 2004, 461-464: 455
[9] Zhang Z G, Niu Y, Zhang X J. Effect of third element Cr in Fe-Cr-Al alloys [J]. J. Iron Steel Res., 2007, 19(7): 46
[9] 张志刚, 牛 焱, 张学军. 铁-铬-铝合金中铬的第三组元作用 [J]. 钢铁研究学报, 2007, 19(7): 46
[10] Gao J, Li B, Wu S X, et al. Relations between the actions of yttrium inhibiting brittleness and the contents of chromium and yttrium in FeCrAl alloys [J]. Met. Funct. Mater., 1998, 6(1): 29
[10] 高 军, 李 碚, 吴双霞等. 钇抑制FeCrAl合金脆性的作用与合金中铬、钇含量的关系 [J]. 金属功能材料, 1998, 6(1): 29
[11] Sun Z Q, Bei H B, Yukinori Y. Microstructural control of FeCrAl alloys using Mo and Nb additions [J]. Mater. Charact., 2017, 132: 126
[12] Liu J M, Liang J Y. Effect of alloying elements on corrosion resistance of ferritic stainless steel [J]. Shanxi Metall., 2005, 32(4): 9
[12] 刘继明, 梁建宇. 合金元素对铁素体不锈钢抗腐蚀性能的影响 [J]. 山西冶金, 2005, 32(4): 9
[13] Li X, Lu X L, Bi H Y. Effect of Nb, Ti on the properties of 15Cr ferritic stainless steel [A]. Proceedings of the 8th (2011) China Iron and Steel Annual Conference [C]. Beijing: Metallurgical Industry Press, 2012: 1
[13] 李 鑫, 陆晓莉, 毕洪运. Nb、Ti对15Cr铁素体不锈钢性能的影响 [A]. 第八届(2011)中国钢铁年会论文集 [C]. 北京: 冶金工业出版社, 2012: 1
[14] Liu Z B. Effect of Nb on microstructure and properties of 00Crl2Ti ferritic stainless steel [D]. Lanzhou: Lanzhou University of Technology, 2011
[14] 刘兆彬. Nb对00Cr12Ti铁素体不锈钢组织和性能的影响 [D]. 兰州: 兰州理工大学, 2011
[15] Kestens L, Jonas J J. Modelling texture change during the static recrystallization of a cold rolled and annealed ultra low carbon steel previously warm rolled in the ferrite region [J]. ISIJ Int., 1997, 37: 807
[16] Yan H T, Bi H Y, Li X, et al. Influence of Nb on microstructure and mechanical properties of 0Cr11 ferritic stainless steel [J]. Iron Steel, 2009, 44(1): 59
[16] 颜海涛, 毕洪运, 李 鑫等. Nb对0Cr11铁素体不锈钢组织和性能的影响 [J]. 钢铁, 2009, 44(1): 59
[17] Fujita N, Ohmura K, Yamamoto A. Changes of microstructures and high temperature properties during high temperature service of Niobium added ferritic stainless steels [J]. Mater. Sci. Eng., 2003, A351: 272
[18] Yamamoto Y, Pint B A, Terrani K A, et al. Development and property evaluation of nuclear grade wrought FeCrAl fuel cladding for light water reactors [J]. J. Nucl. Mater., 2015, 467: 703
[19] Li J. The researches into the grain refinement and corrosion resisting property of the ferritic stainless steel [D]. Chongqing: Chongqing University, 2005
[19] 李 江. 铁素体不锈钢晶粒细化及耐腐蚀性研究 [D]. 重庆: 重庆大学, 2005
[20] Ye F C. Study on surface insulation and oxidation mechanism of FeCrAl electrothermal alloy [D]. Hangzhou: Zhejiang Sci-Tech University, 2010
[20] 叶逢春. 铁铬铝电热合金表面绝缘及抗氧化机理研究 [D]. 杭州: 浙江理工大学, 2010
[21] Lu Y X, Chen W X, Eadie R. The sulfidation/oxidation resistance of Two Ni-Cr-Al-Y alloys at 700 ℃ [J]. Acta Metall. Sin. (Eng. Lett., 2004, 17: 166
[22] Birks N, Meier G H, Pettit F S. Introduction to the High-Temperature Oxidation of Metals [M]. London, UK: Edward Arnold Ltd., 1983: 1
[23] Quadakkers W J, Holzbrecher H, Briefs K G, et al. Differences in growth mechanisms of oxide scales formed on ODS and conventional wrought alloys [J]. Oxid. Met., 1989, 32: 67
[24] Kitaoka S. Mass transfer in polycrystalline alumina under oxygen potential gradients at high temperatures [J]. J. Ceram. Soc. Jpn., 2016, 124: 1100
[25] You P F. Preparation and high temperature performance of NiFe2O4 spinel coating for ferritic stainless steel [D]. Hefei: University of Science and Technology of China, 2018
[25] 游彭飞. SOFC铁素体不锈钢连接体用NiFe2O4基涂层的制备与高温性能 [D]. 合肥: 中国科学技术大学, 2018
[26] Cheng X Y, Wan X J, Shen J N. The effect of Nb on the oxidation behavior of TiAl alloy at high temperature [J]. J. Chin. Soc. Corros. Prot., 2002, 22(2): 69
[26] 程晓英, 万晓景, 沈嘉年. 合金元素Nb在TiAl高温氧化行为中的作用 [J]. 中国腐蚀与防护学报, 2002, 22(2): 69
[27] Zheng H Z, Lu S Q, Wang K L, et al. Effect of phase constitution on oxidation behavior of Cr-Nb alloys [J]. Chin. J. Nonferrous Met., 2008, 18: 2172
[27] 郑海忠, 鲁世强, 王克鲁等. 相组成对Cr-Nb合金高温氧化行为的影响 [J]. 中国有色金属学报, 2008, 18: 2172
[28] Zhang T B, Ding H, Deng Z H, et al. Synergistic effect of Nb and Mo on oxidation behavior of TiAl-based alloys [J]. Rare Met. Mater. Eng., 2012, 41(1): 33
[28] 张铁邦, 丁 浩, 邓志海等. Nb、Mo对TiAl基合金高温氧化行为的协同效应研究 [J]. 稀有金属材料与工程, 2012, 41(1): 33
[1] 耿遥祥, 樊世敏, 简江林, 徐澍, 张志杰, 鞠洪博, 喻利花, 许俊华. 选区激光熔化专用AlSiMg合金成分设计及力学性能[J]. 金属学报, 2020, 56(6): 821-830.
[2] 曹凤婷, 魏洁, 董俊华, 柯伟, 王铁钢, 范其香. 羟基亚乙基二膦酸对20SiMn钢在含Cl-混凝土模拟孔隙液中的缓蚀行为[J]. 金属学报, 2020, 56(6): 898-908.
[3] 魏洁, 魏英华, 李京, 赵洪涛, 吕晨曦, 董俊华, 柯伟, 何小燕. 带损伤环氧涂层钢筋在Cl-和碳化耦合作用下的腐蚀行为[J]. 金属学报, 2020, 56(6): 885-897.
[4] 赵燕春, 毛雪晶, 李文生, 孙浩, 李春玲, 赵鹏彪, 寇生中. Fe-15Mn-5Si-14Cr-0.2C非晶钢微观组织与腐蚀行为[J]. 金属学报, 2020, 56(5): 715-722.
[5] 李秀程,孙明煜,赵靖霄,王学林,尚成嘉. 铁素体-贝氏体/马氏体双相钢中界面的定量化晶体学表征[J]. 金属学报, 2020, 56(4): 653-660.
[6] 蒋一,程满浪,姜海洪,周庆龙,姜美雪,江来珠,蒋益明. 高强度含NNi奥氏体不锈钢08Cr19Mn6Ni3Cu2N (QN1803)的显微组织及性能[J]. 金属学报, 2020, 56(4): 642-652.
[7] 刘振宝,梁剑雄,苏杰,王晓辉,孙永庆,王长军,杨志勇. 高强度不锈钢的研究及发展现状[J]. 金属学报, 2020, 56(4): 549-557.
[8] 杨柯,史显波,严伟,曾云鹏,单以银,任毅. 新型含Cu管线钢——提高管线耐微生物腐蚀性能的新途径[J]. 金属学报, 2020, 56(4): 385-399.
[9] 陈芳,李亚东,杨剑,唐晓,李焰. X80钢焊接接头在模拟天然气凝析液中的腐蚀行为[J]. 金属学报, 2020, 56(2): 137-147.
[10] 马小强,杨坤杰,徐喻琼,杜晓超,周建军,肖仁政. 金属Nb级联碰撞的分子动力学模拟[J]. 金属学报, 2020, 56(2): 249-256.
[11] 姚美意,张兴旺,侯可可,张金龙,胡鹏飞,彭剑超,周邦新. Zr-0.75Sn-0.35Fe-0.15Cr合金在250 ℃去离子水中的初期腐蚀行为[J]. 金属学报, 2020, 56(2): 221-230.
[12] 肖宏,许朋朋,祁梓宸,吴宗河,赵云鹏. 感应加热异温轧制制备钢/铝复合板[J]. 金属学报, 2020, 56(2): 231-239.
[13] 程超,陈志勇,秦绪山,刘建荣,王清江. TA32钛合金厚板的微观组织、织构与力学性能[J]. 金属学报, 2020, 56(2): 193-202.
[14] 王力,董超芳,张达威,孙晓光,Thee Chowwanonthapunya,满成,肖葵,李晓刚. 合金元素对铝合金在泰国曼谷地区初期腐蚀行为的影响[J]. 金属学报, 2020, 56(1): 119-128.
[15] 李鑫,董月成,淡振华,常辉,方志刚,郭艳华. 等通道角挤压制备超细晶纯Ti的腐蚀性能研究[J]. 金属学报, 2019, 55(8): 967-975.