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金属学报  2021, Vol. 57 Issue (7): 845-859    DOI: 10.11900/0412.1961.2020.00378
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基于多尺度力学实验的氢脆现象的最新研究进展
兰亮云1,2(), 孔祥伟1,2, 邱春林3, 杜林秀3
1.东北大学 机械工程与自动化学院 沈阳 110819
2.东北大学 航空动力装备振动及控制教育部重点实验室 沈阳 110819
3.东北大学 轧制技术及连轧自动化国家重点实验室 沈阳 110819
A Review of Recent Advance on Hydrogen Embrittlement Phenomenon Based on Multiscale Mechanical Experiments
LAN Liangyun1,2(), KONG Xiangwei1,2, QIU Chunlin3, DU Linxiu3
1.School of Mechanical Engineering and Automation, Northeastern University, Shenyang 110819, China
2.Key Laboratory of Vibration and Control of Aero-Propulsion System, Ministry of Education of China, Northeastern University, Shenyang 110819, China
3.State Key Laboratory of Rolling Technology and Automation, Northeastern University, Shenyang 110819, China
引用本文:

兰亮云, 孔祥伟, 邱春林, 杜林秀. 基于多尺度力学实验的氢脆现象的最新研究进展[J]. 金属学报, 2021, 57(7): 845-859.
Liangyun LAN, Xiangwei KONG, Chunlin QIU, Linxiu DU. A Review of Recent Advance on Hydrogen Embrittlement Phenomenon Based on Multiscale Mechanical Experiments[J]. Acta Metall Sin, 2021, 57(7): 845-859.

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摘要: 

氢作为新型载能体在未来能源市场占据举足轻重的地位，然而金属材料的氢脆现象却成为阻碍氢能发展的主要瓶颈。由于原子氢在材料内部的固有本质(如可快速扩散、跨尺度分布以及不稳定性等)，氢脆问题一直是个悬而未决但又引人入胜的科学问题。近20年来，随着多尺度力学表征技术的发展，冶金学者针对氢脆问题做了大量研究工作。本文基于此，综述了氢脆研究的最新进展：首先简述了表征材料氢脆倾向性的宏观力学尺度实验(如恒载荷、慢应变速率拉伸实验等)并对比分析各自优缺点；其次从介观尺度上分析了氢-压痕法的特点及主要应用范围；最后基于纳米压痕技术、微圆柱压缩和微悬臂梁弯曲以及环境TEM等原位力学实验表征材料在氢条件下的力学响应行为，重点讨论微纳观力学尺度上氢脆本质的最新研究成果；并对比分析不同实验结果，阐明其诠释氢脆机理的对立统一关系。
关键词 ： 氢脆,  多尺度力学实验,  纳米压痕,  位错,  金属材料    
Abstract：

Hydrogen is widely considered to be one of the future clean energy sources. A large scale of production, storage, transportation, and the use of hydrogen-related energy is likely to be escalated in the next few decades. However, the presence of hydrogen seriously deteriorates the mechanical properties of most structural metals, which is a main threat to the hydrogen economy. Although hydrogen embrittlement has been recognized for more than a century, there is still a lack of effective measures to eliminate this embrittlement in the engineering practices and some aspects of fundamental science; the embrittlement mechanism is still poorly understood. Because hydrogen is the lightest element in the universe, it exhibits several unique characteristics like permeability, fast diffusion, and unstable distribution in different scale defects. These characteristics are seriously affected by external stress, temperature, and other environmental factors. Therefore, the drawback of hydrogen embrittlement is still an extremely complex and attractive scientific topic. In the last two decades, with the development of multi-scale mechanical experimental techniques, various new studies on hydrogen embrittlement have been reported and its mechanism is deeply evaluated. Based on these advances, this review reflects on the complexity and importance of this topic. The macro-mechanical tests such as constant load and slow strain rate tensile tests are presented and their advantage and disadvantage on screening the susceptibility of materials to hydrogen embrittlement are compared. Subsequently, the hydrogen-indentation (hardness) method is introduced at the mesoscale to show the hydrogen-induced cracking and its application. Furthermore, the main focus of this review comprises the modern experimental approaches to fine-scale evaluation of the hydrogen-dislocation interaction, with particular emphasis on the nanoindentation pop-in effect, micro-pillar compression and micro-cantilever bending tests, and environmental transmission electron microscope tests. The fundamental principles of these approaches are overviewed, and their contribution to the elucidation of the hydrogen embrittlement mechanism is discussed. For example, the different effects of hydrogen on the mechanical properties and a mechanism similar to the hydrogen effect are proposed based on the micro-pillar compression and micro-cantilever bending tests. Nevertheless, there are still several discrepancies in the hydrogen-dislocation interaction that needs further investigation.
Key words： hydrogen embrittlement    multiscale mechanical experiment    nanoindentation    dislocation    metal material
收稿日期: 2020-09-21     
ZTFLH:  TG111.8  
基金资助:国家自然科学基金项目(51605084);中央高校基本科研业务费项目(N2103021)
作者简介: 兰亮云，男，1983年生，副教授，博士
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https://www.ams.org.cn/CN/10.11900/0412.1961.2020.00378      或      https://www.ams.org.cn/CN/Y2021/V57/I7/845

图1  Fe-3%Si钢(质量分数)在不同充氢条件下的纳米压痕载荷-位移曲线[74]
MaterialLoad conditionHydrogen freeHydrogen condition
Pop-in loadPop-inHydrogen concentrationPop-in loadPop-in
displacementdisplacement
316 stainless1000 μN total~200 μN4-6 nm*(1) 500 mA·cm-2 for 6 h650-700 μN12-20 nm*
steel[89]load(2) 10 mA·cm-2 for 6 h350 μN5-14 nm*
Austenitic5-500 mN total144.2 μN9.8 nm*1.4% (atomic fraction)72 μN11.6 nm*
stainless steel[91]load
Fe single1000 μN with433 μN53 nm*0.3 × 10-6~150 μN~7.5 nm and
crystal[92]100 μN/sand 320 μN*12 nm*
Ni single300 μN with~220 μN50 nm*-1000 mV cathodic~100 μN~12 nm for
crystal[94,95]50 μN/spotentialeach pop-in*
Cu single600 μN330 μN55 nm*-1000/-1150 mV~320 μN~50 nm*
crystal[95]cathodic potential
Fe-3%Si[20]1000/2250 μN*2000 μN43 nm*-1000 mV cathodic840 μN~20 nm*
potential
Pure Al[96,100]350 μN~280 μN100 nm-1250 mV cathodic~80 μN65 nm
potential
718 alloy[102]2500 μN with1250 μN17 nm-1200 mV cathodic940 μN6 nm
8000 μN/s(101) crystalpotential
plane
TWIP steel[104]2000 μN with550 μN38 nm*-2000 mV cathodic380 μN12 nm*
8000 μN/s(111) crystalpotential
plane
表1  纳米压痕分析有/无氢条件下材料的Pop-in效应[20,89,91,92,94~96,100,102,104]
图2  微圆柱压缩和微悬臂梁弯曲中氢与位错相互作用的示意图
图3  有/无氢条件下纯Al中位错形态及启动应力的实验和模拟结果[107](a) morphology of dislocation at the valley stress of 27 MPa and peak stress of 250 MPa when the number of cycles (N) is 659 cyc without hydrogen(b) morphology of dislocation when the number of cycles is from 789 cyc to 917 cyc(c) the shear stress-strain curves of different systems (The inset shows the dependence of critical shear stress (τc) on the concentration of hydrogen and hydrogen-vacancy (VaH) complexes)
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