添加Ti对Fe22Cr5Al3Mo合金在500℃过热蒸汽中腐蚀行为的影响

doi:10.11900/0412.1961.2021.00200

金属学报

2022, Vol. 58

Issue (5): 610-622 DOI: 10.11900/0412.1961.2021.00200

研究论文

本期目录 | 过刊浏览

添加Ti对Fe22Cr5Al3Mo合金在500℃过热蒸汽中腐蚀行为的影响

孙蓉蓉¹, 姚美意¹(

), 林晓冬¹(

), 张文怀¹, 仇云龙², 胡丽娟¹, 谢耀平¹, 杨健³, 董建新⁴, 成国光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.北京科技大学材料科学与工程学院北京 100083
^5.北京科技大学钢铁冶金新技术国家重点实验室北京 100083

Effect of Ti on the Corrosion Behavior of Fe22Cr5Al3Mo Alloy in 500^oC Superheated Steam

SUN Rongrong¹, YAO Meiyi¹(

), LIN Xiaodong¹(

), ZHANG Wenhuai¹, QIU Yunlong², HU Lijuan¹, XIE Yaoping¹, YANG Jian³, DONG Jianxin⁴, CHENG Guoguang⁵

^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.School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China
^5.State Key Laboratory of Advanced Metallurgy, University of Science and Technology Beijing, Beijing 100083, China

引用本文:

孙蓉蓉, 姚美意, 林晓冬, 张文怀, 仇云龙, 胡丽娟, 谢耀平, 杨健, 董建新, 成国光. 添加Ti对Fe22Cr5Al3Mo合金在500℃过热蒸汽中腐蚀行为的影响[J]. 金属学报, 2022, 58(5): 610-622.
Rongrong SUN, Meiyi YAO, Xiaodong LIN, Wenhuai ZHANG, Yunlong QIU, Lijuan HU, Yaoping XIE, Jian YANG, Jianxin DONG, Guoguang CHENG. Effect of Ti on the Corrosion Behavior of Fe22Cr5Al3Mo Alloy in 500^oC Superheated Steam[J]. Acta Metall Sin, 2022, 58(5): 610-622.

全文: PDF(5670 KB) HTML

摘要:

利用真空非自耗电弧炉熔炼了3种Fe22Cr5Al3Mo-xTi (x = 0、0.5、1.0,质量分数,%)合金,在静态高压釜中进行500℃、10.3 MPa过热蒸汽的腐蚀实验。采用XRD、OM、FIB/SEM、EDS和TEM观察分析腐蚀前后样品的显微组织、晶体结构和成分。结果表明,3种合金腐蚀不同时间形成的氧化膜均发生了分层现象,氧化膜外层均为Fe₂O₃,中间层均为hcp-Cr₂O₃,内层均为Al₂O₃；在靠近氧化膜和合金界面处的Al₂O₃膜中存在α-(Fe, Cr)。0Ti、0.5Ti和1.0Ti合金的Cr氧化膜厚度与氧化膜总厚度的比值(R)遵循R_0.5Ti > R_1.0Ti > R_0Ti,这说明与0Ti和1.0Ti相比0.5Ti合金的耐腐蚀性能最优。添加Ti可抑制合金中Cr₂₃C₆第二相的析出,降低合金的氧化膜总厚度,提高保护性hcp-Cr₂O₃膜的厚度,从而提高合金的耐腐蚀性能。

关键词 ： FeCrAl合金, Ti, 腐蚀, 氧化膜, 显微组织

Abstract：

Zirconium alloys can react with water to produce hydrogen under a loss of coolant accident, which can lead to a hydrogen explosion. Therefore, the idea of developing accident tolerant fuel (ATF) is proposed, which involves nuclear fuel and cladding. FeCrAl alloy is a promising candidate material for ATF cladding. Studying the effects of alloying elements on the corrosion behavior and mechanism of FeCrAl alloy can provide a theoretical basis and guidance for optimizing its composition. Therefore, in this study, the effect of Ti on the corrosion behavior of Fe22Cr5Al3Mo alloy in 500^oC superheated steam was investigated. Three types of Fe22Cr5Al3Mo-xTi (x = 0, 0.5, 1.0, mass fraction, %) alloys, designated as 0Ti, 0.5Ti, and 1.0Ti alloys, respectively, were fabricated and corroded in 500^oC and 10.3 MPa superheated steam using a static autoclave. The microstructure, crystal structure and composition of the samples before and after corrosion were observed using XRD, OM, FIB/SEM, EDS, and TEM. The results show that the oxide films formed on the Fe22Cr5Al3Mo-xTi alloys in 500^oC and 10.3 MPa superheated steam present a trilayer structure consisting of an outer oxide layer of Fe₂O₃, a middle layer of hcp-Cr₂O₃, and an inner layer of Al₂O₃. There is α-(Fe, Cr) in the Al₂O₃ layer near the oxide/metal interface. The ratio, R, of Cr oxide film thickness to total oxide film thickness for 0Ti, 0.5Ti, and 1.0Ti alloys follows the order R_0.5Ti > R_1.0Ti > R_0Ti, which may explain the better corrosion resistance of 0.5Ti alloy than 1.0Ti and 0Ti alloys. The addition of Ti can reduce the total thickness of the oxide films and improve the corrosion resistance of the alloys by increasing the thickness of the protective hcp-Cr₂O₃ film and inhibiting the precipitation of Cr₂₃C₆.

Key words： FeCrAl alloy Ti corrosion oxide film microstructure

收稿日期: 2021-05-12

ZTFLH:

TG142.1

基金资助:国家自然科学基金项目(51871141)

作者简介: 姚美意, yaomeiyi@shu.edu.cn,主要从事核燃料包壳材料锆合金和容错燃料(ATF)包壳材料的研究林晓冬, xdlin@shu.edu.cn,主要从事核电关键结构材料的辐照损伤和腐蚀行为研究
孙蓉蓉,女,1993年生,博士

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	胡丽娟
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	杨健
	董建新
	成国光
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https://www.ams.org.cn/CN/10.11900/0412.1961.2021.00200 或 https://www.ams.org.cn/CN/Y2022/V58/I5/610

表1 实验用合金的成分 (mass fraction / %)

图1 0Ti、0.5Ti和1.0Ti合金的OM像

图2 0Ti、0.5Ti和1.0Ti合金的XRD谱

Alloy	Crystal plane index (hkl)						$a ¯$ / nm
	(110)		(200)		(211)
	2θ / (°)	d / nm	2θ / (°)	d / nm	2θ / (°)	d / nm
α-Fe	44.67	0.20268	65.02	0.14332	82.33	0.11702	0.28664
0Ti	44.15	0.20495	64.24	0.14487	81.45	0.11807	0.28960
0.5Ti	44.18	0.20482	64.24	0.14487	81.42	0.11810	0.28956
1.0Ti	44.28	0.20439	64.36	0.14463	81.42	0.11810	0.28920

表2 α-Fe、0Ti、0.5Ti和1.0Ti合金的XRD特征峰参数(衍射半角θ、晶面间距d)和晶格常数平均值(a¯)

图3 0Ti、0.5Ti和1.0Ti合金中典型第二相粒子的TEM像和SAED花样

表3 0Ti、0.5Ti和1.0Ti合金中典型第二相的尺寸统计 (nm)

图4 0.5Ti和1.0Ti合金500℃、10.3 MPa过热蒸汽中腐蚀1000 h时基体中TiN第二相的EDS面扫描图

图5 0Ti、0.5Ti和1.0Ti合金在500℃、10.3 MPa过热蒸汽中腐蚀3、500和1000 h的氧化膜表面显微组织SEM像

图6 0Ti、0.5Ti和1.0Ti合金在500℃、10.3 MPa过热蒸汽中腐蚀3、500和1000 h的氧化膜截面HAADF像

表4 0Ti、0.5Ti和1.0Ti合金在500℃、10.3 MPa过热蒸汽中腐蚀3、500和1000 h时氧化膜的厚度 (nm)

图7 0.5Ti合金在500℃、10.3 MPa过热蒸汽中腐蚀1000 h时氧化膜截面的HAADF像和EDS面扫描图

图8 0Ti、0.5Ti和1.0Ti合金在500℃、10.3 MPa过热蒸汽中腐蚀500和1000 h的氧化膜截面不同区域的TEM像及SAED花样

表5 0Ti、0.5Ti和1.0Ti合金在500℃、10.3 MPa过热蒸汽中腐蚀3、500和1000 h时的氧化膜晶体结构

图9 FeCrAl合金在500℃过热蒸汽中的腐蚀过程示意图

表6 0Ti、0.5Ti和1.0Ti合金在500℃、10.3 MPa过热蒸汽中腐蚀500 h时铁氧化物膜、铬氧化物膜、铝氧化物膜以及Cr和Al的混合氧化物区的厚度 (nm)

表7 0Ti、0.5Ti和1.0Ti合金在500℃、10.3 MPa过热蒸汽中腐蚀3、500和1000 h时Cr氧化物膜厚度/氧化膜总厚度的比值

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 doi: 10.1016/j.jnucmat.2013.12.005
2	Little E A, Stow D A. Void-swelling in irons and ferritic steels: II. An experimental survey of materials irradiated in a fast reactor [J]. J. Nucl. Mater., 1979, 87: 25 doi: 10.1016/0022-3115(79)90123-5
3	Lim J, Hwang I S, Kim J H. Design of alumina forming FeCrAl steels for lead or lead-bismuth cooled fast reactors [J]. J. Nucl. Mater., 2013, 441: 650 doi: 10.1016/j.jnucmat.2012.04.006
4	Pint B A, Terrani K A, Yamamoto Y, et al. Material selection for accident tolerant fuel cladding [J]. Metall. Mater. Trans., 2015, 2: 190
5	Lim J, Nam H O, Hwang I S, et al. A study of early corrosion behaviors of FeCrAl alloys in liquid lead-bismuth eutectic environments [J]. J. Nucl. Mater., 2010, 407: 205 doi: 10.1016/j.jnucmat.2010.10.018
6	Engkvist J, Bexell U, Grehk M, et al. High temperature oxidation of FeCrAl-alloys-influence of Al-concentration on oxide layer characteristics [J]. Mater. Corros., 2009, 60: 876
7	Pint B A, Unocic K A, Terrani K A. Effect of steam on high temperature oxidation behaviour of alumina-forming alloys [J]. Mater. High Temp., 2015, 32: 28 doi: 10.1179/0960340914Z.00000000058
8	Kögler R, Anwand W, Richter A, et al. Nanocavity formation and hardness increase by dual ion beam irradiation of oxide dispersion strengthened FeCrAl alloy [J]. J. Nucl. Mater., 2012, 427: 133 doi: 10.1016/j.jnucmat.2012.04.029
9	Sun Z Q, Bei H B, Yamamoto Y. Microstructural control of FeCrAl alloys using Mo and Nb additions [J]. Mater. Charact., 2017, 132: 126 doi: 10.1016/j.matchar.2017.08.008
10	Dolley E J, Schuster M, Crawford C, et al. Mechanical behavior of FeCrAl and other alloys following exposure to LOCA conditions plus quenching [A]. Proceedings of the 18th International Conference on Environmental Degradation of Materials in Nuclear Power Systems-Water Reactors [C]. Switzerland: Springer International Publishing, 2018: 185
11	Park D J, Kim H G, Park J Y, et al. A study of the oxidation of FeCrAl alloy in pressurized water and high-temperature steam environment [J]. Corros. Sci., 2015, 94: 459 doi: 10.1016/j.corsci.2015.02.027
12	Badini C, Laurella F. Oxidation of FeCrAl alloy: Influence of temperature and atmosphere on scale growth rate and mechanism [J]. Surf. Coat. Technol., 2001, 135: 291 doi: 10.1016/S0257-8972(00)00989-0
13	Rebak R B. Versatile oxide films protect FeCrAl alloys under normal operation and accident conditions in light water power reactors [J]. JOM, 2018, 70: 176 doi: 10.1007/s11837-017-2705-z
14	Chu R. Studies on high-temperature oxidation and its influence mechanism of Fe-Cr-Al alloy [D]. Shenyang: Shenyang Normal University, 2013
14	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
15	Herbelin J M, Mantel M, Cogne J Y. Future trends of FeCrAl alloys for automative catalytic converters to reach mass production [Z]. Germany: Werkstoff-Informationsgesellschaft mbH, Frankfurt am Main, 1997: 79
16	Ning F Q, Wang X, Yang Y, et al. Uniform corrosion behavior of FeCrAl alloys in borated and lithiated high temperature water [J]. J. Mater. Sci. Technol., 2021, 70: 136 doi: 10.1016/j.jmst.2020.07.026
17	Kitajima Y, Hayashi S, Ukai S, et al. The effect of additional elements on oxide scale evolution of Fe-20at.%Cr-10at.%Al alloy at 900℃ in air [J]. Mater. Sci. Forum., 2008, 595-598: 1013 doi: 10.4028/www.scientific.net/MSF.595-598.1013
18	Huang T H, Naumenko D, Song P, et al. Effect of titanium addition on alumina growth mechanism on yttria-containing FeCrAl-base alloy [J]. Oxid. Met., 2018, 90: 671 doi: 10.1007/s11085-018-9861-6
19	Schutze M. Lifetime Modelling of High Temperature Corrosion Processes EFC 34 [M]. Boca Raton, FL, USA: CRC Press, 2001: 66
20	Dang J, Zhou P, Shi H Y. Influence of Nb/Ti on corrosion resistance properties of low chromium ferritic stainless steels [J]. Iron Steel Van Tit, 2020, 41: 147
20	党杰, 周鹏, 史洪源. Nb、Ti对低铬铁素体不锈钢腐蚀性能的影响 [J]. 钢铁钒钛, 2020, 41: 147
21	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 Meeting [C]. Beijing: Metallurgical Industry Press, 2011: 535
21	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, 2011: 535
22	Zhang X, Sun Q S, Du W. Effect of Nb, Ti on structure and property of ultra-low carbon and nitrogen ferritic stainless steel [A]. Proceedings of the 4th Annual Youth Academic Conference of China Society of Metals [C]. Beijing: Iron & Steel, 2008: 138
22	张鑫, 孙全社, 杜伟. Nb、Ti对超低碳氮430铁素体不锈钢组织和性能的影响 [A]. 第4届中国金属学会青年学术年会论文集 [C]. 北京: 钢铁, 2008: 138
23	Yu Y N. Fundamentals of Materials Science [M]. Beijing: Higher Education Press, 2006: 781
23	余永宁. 材料科学基础 [M]. 北京: 高等教育出版社, 2006: 781
24	Qian Y, Sun R R, Zhang W H, et al. Effect of Nb on microstructure and corrosion resistance of Fe22Cr5Al3Mo alloy [J]. Acta Metall. Sin., 2020, 56: 321
24	钱月, 孙蓉蓉, 张文怀等. Nb对Fe22Cr5Al3Mo合金显微组织和耐腐蚀性能的影响 [J]. 金属学报, 2020, 56: 321
25	Li N, Parker S S, Wood E S, et al. Oxide morphology of a FeCrAl alloy, Kanthal APMT, following extended aging in air at 300^oC to 600^oC [J]. Metall. Mater. Trans., 2018, 49A: 2940
26	Li N, Parker S S, Saleh T A, et al. Intermediate temperature corrosion behaviour of Fe-12Cr-6Al-2Mo-0.2Si-0.03Y alloy (C26M) at 300-600^oC [J]. Corros. Sci., 2019, 157: 274 doi: 10.1016/j.corsci.2019.05.029
27	Dai J X, Gong Z M, Xu S T, et al. In situ study on the initial oxidation behavior of zirconium alloys with near-ambient pressure XPS [J]. Acta Phys. Chim. Sin., 2020, 36: 2003026
27	戴久翔, 龚忠苗, 徐诗彤等. 锆合金初始氧化行为的原位近常压XPS研究 [J]. 物理化学学报, 2020, 36: 2003026
28	Pan D, Zhang R Q, Wang H J, et al. In steam short-time oxidation kinetics of FeCrAl alloys [J]. J. Mater. Eng. Perform., 2018, 27: 6407 doi: 10.1007/s11665-018-3665-3
29	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: 46
29	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: 46
30	Terrani K A, Pint B A, Kim Y J, et al. Uniform corrosion of FeCrAl alloys in LWR coolant environments [J]. J. Nucl. Mater., 2016, 479: 36 doi: 10.1016/j.jnucmat.2016.06.047
31	Pint B A, Terrani K A, Rebak R B. Steam oxidation behavior of FeCrAl cladding [A]. Proceedings of the 18th International Conference on Environmental Degradation of Materials in Nuclear Power Systems-Water Reactors [C]. Switzerland: Springer International Publishing, 2018: 235

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