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金属学报  2018, Vol. 54 Issue (11): 1503-1524    DOI: 10.11900/0412.1961.2018.00342
  组织与结构 本期目录 | 过刊浏览 |
高温合金中硼化物精细结构的高空间分辨电子显微学研究
马秀良(), 胡肖兵
中国科学院金属研究所 沈阳 110016
High-Resolution Transmission Electron Microscopic Study of Various Borides Precipitated in Superalloys
Xiuliang MA(), Xiaobing HU
Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
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摘要: 

为了提高高温服役性能,微量元素B被广泛加入到几乎所有的商用高温合金中。研究人员普遍认为B倾向于在晶界偏析,这种偏析有助于抑制高温下晶界的迁移。B在高温合金中有2种存在形式,一种是以固溶形式存在,另一种是以硼化物析出相的形式出现。B在高温合金中的固溶度非常低,故在高温服役过程中会析出多种硼化物,如M2B、M3B2M5B3。尽管这些硼化物在高温合金中普遍存在,但人们对于其认识仍停留在形貌特征等相对宏观的尺度上。而基于这些析出相精细结构的深入认识有助于人们优化材料设计及合理的阐述结构-性能关系。近年来,基于像差校正电子显微技术,本课题组利用多种先进的电子显微学方法在原子尺度上对以上3种硼化物进行了系统的微结构解析。本文概述了硼化物的研究现状,系统介绍了对硼化物结构与缺陷的新认识,并展望了相关研究趋势。

关键词 高温合金硼化物晶体学特征多面体堆垛透射电子显微术    
Abstract

Microelement B is widely added into almost all commercial superalloys because B contributes to strengthening grain boundaries at high temperature during service. Generally, B is present in two different forms. Besides the solute state in matrix, B tends to react with transition elements at high temperatures, giving rise to various borides including M2B, M3B2 and M5B3 phases. An accurate knowledge of the microstructural characterizations of these borides is of great importance for a better understanding of the structure-property relationship and designing materials with improved properties. By means of various advanced techniques based on the aberration-corrected transmission electron microscopy (TEM), microstructural features of above borides have been systematically investigated. Various defect features which were controversial in the past have been clarified. In this paper, after a brief review on the studies of borides, the atomic-scale information on the microstructural features has been presented. Finally, some prospects for future studies have been proposed.

Key wordssuperalloy    boride    crystallographic feature    polyhedral stacking    transmission electron microscopy
收稿日期: 2018-07-23     
ZTFLH:  TG146.1  
基金资助:国家重点基础研究发展计划项目Nos.2009CB623705和 2010CB631206,以及国家自然科学基金项目No.11327901
作者简介:

作者简介 马秀良,男,1964年生,研究员,博士

引用本文:

马秀良, 胡肖兵. 高温合金中硼化物精细结构的高空间分辨电子显微学研究[J]. 金属学报, 2018, 54(11): 1503-1524.
Xiuliang MA, Xiaobing HU. High-Resolution Transmission Electron Microscopic Study of Various Borides Precipitated in Superalloys. Acta Metall Sin, 2018, 54(11): 1503-1524.

链接本文:

https://www.ams.org.cn/CN/10.11900/0412.1961.2018.00342      或      https://www.ams.org.cn/CN/Y2018/V54/I11/1503

Structure Space group Lattice parameter Atom (Wyckoff Fractional coordinate
nm position) x y z
W2B I4/mcm a=0.56 W (8h) 0.169 0.669 0.000
C16 (No.140) c=0.47 B (4a) 0.000 0.000 0.250
V3B2 P4/mbm a=0.57 V (4h) 0.173 0.673 0.500
D5a (No.127) c=0.30 V (2a) 0.000 0.000 0.000
B (4g) 0.388 0.888 0.000
Cr5B3 I4/mcm a=0.55 Cr (16l) 0.166 0.666 0.150
D81 (No.140) c=1.06 Cr (4c) 0.000 0.000 0.000
B (8h) 0.625 0.125 0.000
B (4a) 0.000 0.000 0.250
表1  W2B、V3B2、Cr5B3晶体学信息[32]
图1  M3B2 (D5a)、M5B3 (D81)、M2B (C16)的单胞示意图[32]
Structure Space group Lattice parameter Atom (Wyckoff Fractional coordinate
nm position) x y z
Cr2B I4/mcm a=0.52 Cr (8h) 0.167 0.667 0.000
C16 (No.140) c=0.43 B (4a) 0.000 0.000 0.250
Cr2B Fddd a=1.47 Cr (16e) 0.917 0.000 0.000
Cb (No.70) b=0.74 Cr (16f) 0.000 0.333 0.000
c=0.43 B (16e) 0.373 0.000 0.000
Cr2B P6222 a=0.43 Cr (6f) 0.500 0.000 0.390
Ca (No.180) c=1.09 Cr (6j) 0.166 0.332 0.500
β=120° B (3a) 0.000 0.000 0.333
B (3c) 0.500 0.500 0.333
表2  C16-、Cb-和Ca-Cr2B的晶体结构信息[33]
图2  反四棱柱的体式图
图3  C16、Cb、Ca结构之间的联系,Cb结构在[011]Cb、[011?]Cb方向的结构投影,C16结构沿[001]C16方向的投影以及Ca结构在[110]Ca、[100]Ca、[010]Ca方向投影[33]
图4  Ca结构在[100]Ca方向的投影及其简化排列图,C16结构在[001]C16、[11?1]C16方向投影的简化排列图,Cb结构在[001]Cb、[011]Cb方向投影的简化排列图,一种新的N2有序结构的投影简化图[33]
图5  Cr2B多型体的结构衍生图(其中N代表堆垛层数)[33]
图6  M2B型硼化物在基体内(γ /γ’)的析出
图7  通过大角度倾转所获取的系列电子衍射图[31]
图8  通过大角度倾转所获取的系列电子衍射图[31]
图9  包含缺陷的M2B晶粒衍射特征,C16结构在[001]C16、[11?1]C16方向的衍射示意图,Cb结构在[001]Cb、[011]Cb方向的衍射示意图
图10  M2B相的晶内析出及其化学成分组成
图11  C16结构在(110)C16平面内与Cb结构在(100)Cb面内主要方向之间相对位置示意图,及[010]Cb、[11?3]C16晶带轴电子衍射示意图
图12  基体晶粒内析出M2B相的暗场像及EDPs[31]
图13  带有层错的C16结构沿[001]C16方向的HRTEM图[31]
图14  带有层错的C16结构沿[11?0]C16方向的HRTEM图[31]
图15  同一位置、不同倾转角下Cb结构的HRTEM图,及带有层错的Cb结构沿[001]Cb方向的HRTEM图[31]
图16  M2B内复杂共生行为[33]
图17  M2B多型体内的长周期结构[33]
图18  M3B2相的系列电子衍射谱
图19  晶粒内部析出的M3B2相的TEM明场像及EDX谱
图20  M3B2相在[001]、[100]、[110]取向的原子分辨率图像,有序结构模型,有序结构在[001]、[100]、[110]取向的投影结构[32]
图21  M3B2型硼化物中的化学有序[35]
图22  带有缺陷结构的M3B2相在[110]方向HRTEM像
图23  M3B2相中的多面体尺度共生[32]
图24  大角度倾转获取的M5B3相的系列电子衍射图
图25  M5B3相的晶内析出及其化学信息
图26  M5B3相在[001]、[100]、[110]取向的原子分辨率图像,有序结构模型,有序结构在[001]、[100]、[110]取向的投影结构[32]
图27  M5B3型硼化物中的化学有序[35]
图28  带有缺陷结构的M5B3相在[110]方向HRTEM像
图29  M5B3相中的多面体尺度共生[32]
图30  M3B2相与M5B3间的大尺度共生HAADF图像及复合衍射
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