Please wait a minute...
金属学报  2020, Vol. 56 Issue (1): 53-65    DOI: 10.11900/0412.1961.2019.00146
  综述 本期目录 | 过刊浏览 |
(9~12)%Cr马氏体耐热钢中微量B元素的择优分布行为及其对微观组织与力学性能的影响
杨柯1,梁烨1,2,严伟1,3(),单以银1,3
1. 中国科学院金属研究所  沈阳 110016
2. 中国科学技术大学材料科学与工程学院  沈阳 110016
3. 中国科学院金属研究所中国科学院核用材料与安全评价重点实验室  沈阳 110016
Preferential Distribution of Boron and its Effect on Microstructure and Mechanical Properties of (9~12)%Cr Martensitic Heat Resistant Steels
YANG Ke1,LIANG Ye1,2,YAN Wei1,3(),SHAN Yiyin1,3
1. Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
2. School of Materials Science and Engineering, University of Science and Technology of China, Shenyang 110016, China
3. Key Laboratory of Nuclear Materials and Safety Assessment, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
引用本文:

杨柯,梁烨,严伟,单以银. (9~12)%Cr马氏体耐热钢中微量B元素的择优分布行为及其对微观组织与力学性能的影响[J]. 金属学报, 2020, 56(1): 53-65.
Ke YANG, Ye LIANG, Wei YAN, Yiyin SHAN. Preferential Distribution of Boron and its Effect on Microstructure and Mechanical Properties of (9~12)%Cr Martensitic Heat Resistant Steels[J]. Acta Metall Sin, 2020, 56(1): 53-65.

全文: PDF(4425 KB)   HTML
摘要: 

(9~12)%Cr钢中添加微量B元素可显著抑制M23C6碳化物的熟化,从而提高蠕变强度,增加蠕变断裂寿命。钢中B元素的择优分布行为是其充分发挥积极作用的关键,也是深入研究其作用机理的前提,一直是(9~12)%Cr马氏体耐热钢领域的研究热点。本文简述了B元素对钢力学性能的影响,介绍了表征钢中微量B元素分布的常用实验手段。在阐述B元素在钢中的物理冶金学原理以及固溶与扩散机制的基础上,重点讨论了B元素在(9~12)%Cr马氏体耐热钢中的择优分布行为及其影响因素。最后对目前微量B元素抑制马氏体耐热钢中M23C6碳化物熟化的2种机理进行了梳理,系统地阐述了B元素的择优分布行为与其抑制M23C6碳化物熟化、提高蠕变性能的积极作用之间的关系,深化对B元素在(9~12)%Cr马氏体耐热钢中的作用机理的认识。

关键词 马氏体耐热钢B偏聚M23C6碳化物Ostwald熟化    
Abstract

Addition of small amount of boron (B) in the (9~12)%Cr martensitic heat resistant steels can obviously prohibit the Ostwald ripening of M23C6 carbides so as to improve creep strength as well as creep rupture life. With the purpose of taking full advantages of B element, it is critical to make B preferentially distribute in (9~12)%Cr martensitic heat resistant steels. The mechanism of B preventing M23C6 carbides from ripening is also on the premise of clearly identifying the preferential distribution of B in the steels. Much concern has been growing over the preferential distribution of B in the research of (9~12)%Cr martensitic heat resistant steels. Therefore, this article gives a review on this aspect. Following a summary of the effect of B on mechanical properties, several commonly used characterizing methods for B segregation in the steels are introduced. Based on the physical metallurgy and the solution, diffusion mechanisms of B element, discussions on the preferential distribution of B element at prior austenite grain boundaries and in the M23C6 carbides as well as the related factors are emphasized. At last, two prevalent mechanisms of B restraining the coarsening of M23C6 carbides in (9~12)%Cr martensitic heat resistant steels are given by an intensive explanation so that the relationship between the preferential distribution of B and its advantage of increasing creep performance by suppressing the ripening M23C6 carbides are systematically elaborated, which gives a deep understanding of the role of B element in (9~12)%Cr martensitic heat resistant steels.

Key wordsmartensitic heat resistant steel    B    segregation    M23C6 carbide    Ostwald ripening
收稿日期: 2019-05-06     
ZTFLH:  TG142.1  
基金资助:国家重点研发计划项目(2017YFB0305201);国家自然科学基金项目(51971226)
作者简介: 杨 柯,男,1961年生,研究员
图1  热处理态G115钢中的硼化物
图2  不同温度时效1000 h后G115钢中B元素的分布
图3  700 ℃时效1000 h后G115钢中发生熟化的M23C6碳化物
图4  利用原子探针层析术(APT)获得的原奥氏体晶界处M23C6碳化物的原子三维重构图[8]
图5  热处理过程中M23(CB)6的形成过程示意图[10]
图6  B抑制M23C6碳化物熟化机理图[9]
[1] Liu Z D, Cheng S C, Bao H S, et al. Localization of boiler steel technology in China used for ultra super critical power plants [J]. Iron Steel, 2009, 44(6): 1
[1] (刘正东, 程世长, 包汉生等. 超超临界火电机组用锅炉钢技术国产化问题 [J]. 钢铁, 2009, 44(6): 1)
[2] Li W W. Research on the mechanism design and evaluation method of power coal supply chain's coordination under uncertainty conditions [D]. Harbin: Harbin Institute of Technology, 2016
[2] (李巍巍. 不确定条件下电煤供应链协调的机制设计及评价方法研究 [D]. 哈尔滨: 哈尔滨工业大学, 2016)
[3] Shu G G, Liu J N, Shi C Z, et al. Microstructure, Mechanical Properties and Engineering Application of T/P91 Heat Resistant Steel for Supercritical Power Plants [M]. Xi'an: Shanxi Science and Technology Press, 2006: 9
[3] (束国刚, 刘江南, 石崇哲等. 超临界锅炉用T/P91钢的组织性能与工程应用 [M]. 西安: 陕西科学技术出版社, 2006: 9)
[4] Msuyama F. History of power plants and progress in heat resistant steels [J]. ISIJ Int., 2001, 41: 612
[5] Maruyama K, Sawada K, Koike J I. Strengthening mechanisms of creep resistant tempered martensitic steel [J]. ISIJ Int., 2001, 41: 641
[6] Abe F. Research and development of heat-resistant materials for advanced USC power plants with steam temperatures of 700 ℃ and above [J]. Engineering, 2015, 1: 211
[7] Yan P, Liu Z D, Bao H S, et al. Effect of normalizing temperature on the strength of 9Cr-3W-3Co martensitic heat resistant steel [J]. Mater. Sci. Eng., 2014, A597: 148
[8] Liu F, Fors D H R, Golpayegani A, et al. Effect of boron on carbide coarsening at 873 K (600 ℃) in 9 to 12 pct chromium steels [J]. Metall. Mater. Trans., 2012, 43A: 4053
[9] Abe F. Behavior of boron in 9Cr heat resistant steel during heat treatment and creep deformation [J]. Key Eng. Mater., 2007, 345-346: 569
[10] Abe F. Precipitate design for creep strengthening of 9%Cr tempered martensitic steel for ultra-supercritical power plants [J]. Sci. Technol. Adv. Mater., 2008, 9: 013002
[11] Abe F. Effect of boron on microstructure and creep strength of advanced ferritic power plant steels [J]. Procedia Eng., 2011, 10: 94
[12] Titova T I, Shulgan N A, Malykhina I Y. Effect of boron microalloying on the structure and hardenability of building steel [J]. Met. Sci. Heat Treat., 2007, 49: 39
[13] Grange R A, Garvey T M. Factors affecting the hardenability of boron-treated steels [J]. Trans. Am. Soc. Met., 1946, 37: 136
[14] Maitrepierre P, Thivellier D, Tricot R. Influence of boron on the decomposition of austenite in low carbon alloyed steels [J]. Metall. Mater. Trans., 1975, 6A: 287
[15] Hwang B, Suh D W, Kim S J. Austenitizing temperature and hardenability of low-carbon boron steels [J]. Scr. Mater., 2011, 64: 1118
[16] Karlsson L, Nordén H, Odelius H. Non-equilibrium grain boundary segregation of boron in austenitic stainless steel—I. Large scale segregation behaviour [J]. Acta Metall., 1988, 36: 1
[17] Asahi H. Effects of Mo addition and austenitizing temperature on hardenability of low alloy B-added steels [J]. ISIJ Int., 2002, 42: 1150
[18] Li X L. The segregations of boron and niobium at grain boundaries in microalloyed steel and high-purity nickel [D]. Beijing: University of Science and Technology Beijing, 2017
[18] (李向龙. 硼、铌元素在微合金钢与高纯镍中的晶界偏聚行为 [D]. 北京: 北京科技大学, 2017)
[19] Kapadia B M. Effect of boron additions on the toughness of heat-treated low-alloy steels [J]. J. Heat Treat., 1987, 5: 41
[20] Ghali S N, El-Faramawy H S, Eissa M M. Influence of boron additions on mechanical properties of carbon steel [J]. J. Miner. Mater. Charact. Eng., 2012, 11: 995
[21] Yan P, Liu Z D, Bao H S, et al. Effect of microstructural evolution on high-temperature strength of 9Cr-3W-3Co martensitic heat resistant steel under different aging conditions [J]. Mater. Sci. Eng., 2013, A588: 22
[22] Shirzadi A, Jackson S. Structural Alloys for Power Plants [M]. Cambridge: Woodhead Publishing, 2014: 250
[23] Golpayegani A, Liu F, Svensson H, et al. Microstructure of a creep-resistant 10 pct chromium steel containing 250 ppm boron [J]. Metall. Mater. Trans., 2011, 42A: 940
[24] H?ttestrand M, Andrén H O. Boron distribution in 9-12% chromium steels [J]. Mater. Sci. Eng., 1999, A270: 33
[25] Mayr P, Martín F M, Albu M, et al. Correlation of creep strength and microstructural evolution of a boron alloyed 9Cr3W3CoVNb steel in as-received and welded condition [J]. Mater. High Temp., 2010, 27: 67
[26] Horiuchi T, Igarashi M, Abe F. Improved utilization of added B in 9Cr heat-resistant steels containing W [J]. ISIJ Int., 2002, 42(Suppl.1) S67
[27] Mayr P, Holzer I, Mendez-Martin F, et al. Experience with 9Cr3W3CoVNbBN base material and crosswelds at 650 ℃ for implementation in USC power plants [A]. 3rd Symposium on Heat Resistant Steels and Alloys for High Efficiency USC Power Plants [C]. Tsukuba, Japan: National Institute for Materials Science, 2009: 1
[28] Albu M, Mayr P, Martín F M, et al. The influence of boron on the microstructure of a 9 wt% Cr ferritic steel [J]. Mater. High Temp., 2011, 28: 120
[29] Lejcek P. Grain Boundary Segregation in Metals [M]. Berlin: Springer-Verlag Berlin and Heidelberg, 2010: 27
[30] Shigesato G, Fujishiro T, Hara T. Grain boundary segregation behavior of boron in low-alloy steel [J]. Metall. Mater. Trans., 2014, 45A: 1876
[31] He X L, Chu Y Y, Zhang X L, et al. The distribution of boron in steel [J]. Acta Metall. Sin., 1979, 13: 235
[31] (贺信莱, 诸幼义, 张秀林等. 硼在钢中的分布 [J]. 金属学报, 1979, 13: 235)
[32] Jahazi M, Jonas J J. The non-equilibrium segregation of boron on original and moving austenite grain boundaries [J]. Mater. Sci. Eng., 2002, A335: 49
[33] Li W Q, Sun J Y, Xu H X, et al. Application of fission track etching method for study carburized boron steels [J]. Iron Steel, 1992, 27(6): 42
[33] (李文卿, 孙继跃, 许洪新等. 显微径迹照相技术在渗碳硼钢研究中的应用 [J]. 钢铁, 1992, 27(6): 42)
[34] Yin H T, Wang J. SIMS analysis technology and the applied research [J]. Chin. J. Spectrosc. Lab., 2008, 25: 180
[34] (尹会听, 王 洁. 二次离子质谱分析技术及应用研究 [J]. 光谱实验室, 2008, 25: 180)
[35] Li Y J, Ponge D, Choi P, et al. Atomic scale investigation of non-equilibrium segregation of boron in a quenched Mo-free martensitic steel [J]. Ultramicroscopy, 2015, 159: 240
[36] Yong Q L. Secondary Phases in Steels [M]. Beijing: Metallurgical Industry Press, 2006: 167
[36] (雍岐龙. 钢铁材料中的第二相 [M]. 北京: 冶金工业出版社, 2006: 167)
[37] Li P S, Xiao L J, Xie Z. Thermodynamic analysis of AlN and BN competitive precipitation in low carbon steel [J]. J. Iron Steel Res., 2009, 21(5): 16
[37] (李培松, 肖丽俊, 谢 植. 低碳钢中AlN和BN竞相析出热力学分析 [J]. 钢铁研究学报, 2009, 21(5): 16)
[38] Klimenkov M, Materna-Morris E, M?slang A. Boron effect on the microstructure of 9%Cr ferritic-martensitic steels [J]. J. Nucl. Mater., 2015, 462: 280
[39] Busby P E, Wells C. Diffusion of boron in alpha iron [J]. JOM, 1954, 6(9): 972
[40] Wang W D, Zhang S H, He X L. Diffusion of boron in alloys [J]. Acta Metall. Mater., 1995, 43: 1693
[41] Hayashi Y, Sugeno T. Nature of boron in α-iron [J]. Acta Metall., 1970, 18: 693
[42] Fors D H R, Wahnstr?m G. Nature of boron solution and diffusion in α-iron [J]. Phys. Rev., 2008, 77B: 132102
[43] Bialon A F, Hammerschmidt T, Drautz R. Ab initio study of boron in α-iron: Migration barriers and interaction with point defects [J]. Phys. Rev., 2013, 87B: 104109
[44] McLellan R B, Ko C. The diffusion of boron in f.c.c. iron [J]. J. Phys. Chem. Solids, 1993, 54: 465
[45] Busby P E, Warga M E, Wells C. Diffusion and solubility of boron in iron and steel [J]. JOM, 1953, 5(11): 1463
[46] Zhang X, Li X L, Wu P, et al. First principles calculation of boron diffusion in fcc-Fe [J]. Curr. Appl. Phys., 2018, 18: 1108
[47] Takahashi J, Ishikawa K, Kawakami K, et al. Atomic-scale study on segregation behavior at austenite grain boundaries in boron- and molybdenum-added steels [J]. Acta Mater., 2017, 133: 41
[48] Hondros E D, Seah M R, Hofmann S, et al. Physical Metallurgy [M]. 4th Ed., Amsterdam: North-Holland, 1996: 1201
[49] Williams T M, Stoneham A M, Harries D R. The segregation of boron to grain boundaries in solution-treated Type 316 austenitic stainless steel [J]. Met. Sci., 1976, 10: 14
[50] Xu T D, Cheng B Y. Kinetics of non-equilibrium grain-boundary segregation [J]. Prog. Mater. Sci., 2004, 49: 109
[51] Li Y J, Ponge D, Choi P, et al. Segregation of boron at prior austenite grain boundaries in a quenched martensitic steel studied by atom probe tomography [J]. Scr. Mater., 2015, 96: 13
[52] Mun D J, Shin E J, Cho K C, et al. Cooling rate dependence of boron distribution in low carbon steel [J]. Metall. Mater. Trans., 2012, 43A: 1639
[53] Miyamoto G, Goto A, Takayama N, et al. Three-dimensional atom probe analysis of boron segregation at austenite grain boundary in a low carbon steel—Effects of boundary misorientation and quenching temperature [J]. Scr. Mater., 2018, 154: 168
[54] Zhu H Y, Sun J, Wang W, et al. Experimental investigation on segregation and remelting behaviors of boron-containing steel with low carbon [J]. Results Phys., 2019, 12: 67
[55] Chu Y Y, He X L, Tang L, et al. Two kinds of boron segregation at austenite grain boundaries [J]. Acta Metall. Sin., 1987, 23: 169
[55] (褚幼义, 贺信莱, 唐 立等. 硼在奥氏体晶界的两类偏聚 [J]. 金属学报, 1987, 23: 169)
[56] Aust K T, Hanneman R E, Niessen P, et al. Solute induced hardening near grain boundaries in zone refined metals [J]. Acta Metall., 1968, 16: 291
[57] Zhang S H, He X L, Chu Y Y, et al. Behaviour of boron segregation to grain boundaries in bcc Fe-3%Si alloy [J]. Acta Metall. Sin., 1993, 29(6): 1
[57] (章三红, 贺信莱, 褚幼义等. 硼在体心立方Fe-3%Si合金中的晶界偏聚行为 [J]. 金属学报, 1993, 29(6): 1)
[58] Brailsford A D, Bullough R. The rate theory of swelling due to void growth in irradiated metals [J]. J. Nucl. Mater., 1972, 44: 121
[59] Simpson C J, Aust K T, Winegard W C. The formation of Pb2Au precipitates at high velocity grain boundaries after quenching [J]. Metall. Mater. Trans., 1970, 1B: 1482
[60] Watanabe S, Ohtani H, Kunitake T. The Influence of hot rolling and heat treatments on the distribution of boron in steel [J]. Trans. Iron Steel Ins. Jpn., 1983, 23: 31
[61] Gay A S, Fraczkiewicz A, Biscondi M. Mechanisms of the intergranular segregation of boron in (B2) FeAl alloys [J]. Mater. Sci. Forum, 1999, 294-296: 453
[62] Xu T D. Non-equilibrium grain-boundary segregation kinetics [J]. J. Mater. Sci., 1987, 22: 337
[63] Wang H, Yan W, van Zwaag S, et al. On the 650 ℃ thermostability of 9-12Cr heat resistant steels containing different precipitates [J]. Acta Mater., 2017, 134: 143
[64] Hald J. Microstructure and long-term creep properties of 9-12% Cr steels [J]. Int J. Pressure Vessels Piping, 2008, 85: 30
[65] Umantsev A, Olson G B. Ostwald ripening in multicomponent alloys [J]. Scr. Metall. Mater., 1993, 29: 1135
[66] Abe F. Coarsening behavior of lath and its effect on creep rates in tempered martensitic 9Cr-W steels [J]. Mater. Sci. Eng., 2004, A387-389: 565
[67] Takahashi N, Fujita T, Yamada T. Effect of boron on long period creep rupture strength of 12%Cr heat resisting steel [J]. Tetsu Hagané, 1975, 61: 2263
[67] (高橋 紀雄, 藤田 利夫, 山田 武海. 12%Cr耐熱鋼の長時間クリープ破断強度におよぼすBの影響 [J]. 鉄と鋼, 1975, 61: 2263)
[68] H?ttestrand M, Schwind M, Andrén H O. Microanalysis of two creep resistant 9-12% chromium steels [J]. Mater. Sci. Eng., 1998, A250: 27
[69] Lundin L, F?llman S, Andrén H O. Microstructure and mechanical properties of a 10% chromium steel with improved creep resistance at 600 ℃ [J]. Mater. Sci. Technol., 1997, 13: 233
[1] 张雷雷, 陈晶阳, 汤鑫, 肖程波, 张明军, 杨卿. K439B铸造高温合金800℃长期时效组织与性能演变[J]. 金属学报, 2023, 59(9): 1253-1264.
[2] 刘兴军, 魏振帮, 卢勇, 韩佳甲, 施荣沛, 王翠萍. 新型钴基与Nb-Si基高温合金扩散动力学研究进展[J]. 金属学报, 2023, 59(8): 969-985.
[3] 陈润农, 李昭东, 曹燕光, 张启富, 李晓刚. 9%Cr合金钢在含Cl环境中的初期腐蚀行为及局部腐蚀起源[J]. 金属学报, 2023, 59(7): 926-938.
[4] 袁江淮, 王振玉, 马冠水, 周广学, 程晓英, 汪爱英. Cr2AlC涂层相结构演变对力学性能的影响[J]. 金属学报, 2023, 59(7): 961-968.
[5] 张德印, 郝旭, 贾宝瑞, 吴昊阳, 秦明礼, 曲选辉. Y2O3 含量对燃烧合成Fe-Y2O3 纳米复合粉末性能的影响[J]. 金属学报, 2023, 59(6): 757-766.
[6] 冯艾寒, 陈强, 王剑, 王皞, 曲寿江, 陈道伦. 低密度Ti2AlNb基合金热轧板微观组织的热稳定性[J]. 金属学报, 2023, 59(6): 777-786.
[7] 王福容, 张永梅, 柏国宁, 郭庆伟, 赵宇宏. Al掺杂Mg/Mg2Sn合金界面的第一性原理计算[J]. 金属学报, 2023, 59(6): 812-820.
[8] 赵亚峰, 刘苏杰, 陈云, 马会, 马广财, 郭翼. 铁素体-贝氏体双相钢韧性断裂过程中的夹杂物临界尺寸及孔洞生长[J]. 金属学报, 2023, 59(5): 611-622.
[9] 廖京京, 张伟, 张君松, 吴军, 杨忠波, 彭倩, 邱绍宇. Zr-Sn-Nb-Fe-V合金在过热蒸汽中的周期性钝化-转折行为[J]. 金属学报, 2023, 59(2): 289-296.
[10] 李斗, 徐长江, 李旭光, 李双明, 钟宏. La掺杂PCeyFe3CoSb12 热电材料及涂层的热电性能[J]. 金属学报, 2023, 59(2): 237-247.
[11] 王虎, 赵琳, 彭云, 蔡啸涛, 田志凌. 激光熔化沉积TiB2 增强TiAl基合金涂层的组织及力学性能[J]. 金属学报, 2023, 59(2): 226-236.
[12] 姜江, 郝世杰, 姜大强, 郭方敏, 任洋, 崔立山. NiTi-Nb原位复合材料的准线性超弹性变形[J]. 金属学报, 2023, 59(11): 1419-1427.
[13] 胡敏, 周生玉, 国京元, 胡明昊, 李冲, 李会军, 王祖敏, 刘永长. 多相Ni3Al基高温合金微区氧化行为[J]. 金属学报, 2023, 59(10): 1346-1354.
[14] 段慧超, 王春阳, 叶恒强, 杜奎. 纳米多孔金属表面结构与成分的三维电子层析表征[J]. 金属学报, 2023, 59(10): 1291-1298.
[15] 孙腾腾, 王洪泽, 吴一, 汪明亮, 王浩伟. 原位自生2%TiB2 颗粒对2024Al增材制造合金组织和力学性能的影响[J]. 金属学报, 2023, 59(1): 169-179.