Fe?Mn?(Al)?C高強韌性鋼氫脆微觀機制的研究進展

章小峰; 萬亞雄; 武學俊; 闞中偉; 黃貞益

doi:10.13374/j.issn2095-9389.2019.11.05.005

Fe?Mn?(Al)?C高強韌性鋼氫脆微觀機制的研究進展

doi: 10.13374/j.issn2095-9389.2019.11.05.005

章小峰^{1, 2, ,},
萬亞雄^{1, 2},
武學俊^{1, 2},
闞中偉^{1, 2},
黃貞益^{1, 2}

1.
冶金工程與資源綜合利用安徽省重點實驗室（安徽工業大學），馬鞍山 243002
2.
安徽工業大學冶金工程學院，馬鞍山 243002

基金項目: 國家自然科學基金資助項目（51674004）

詳細信息

通訊作者:
E-mail: egzxf@ahut.edu.cn

中圖分類號: TG142.1
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- 文章訪問數: 2439
- HTML全文瀏覽量: 1944
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- 被引次數: 0
出版歷程
- 收稿日期: 2019-11-05
- 刊出日期: 2020-09-11

Research progress toward hydrogen embrittlement microstructure mechanism in Fe–Mn–(Al)–C high-strength-and-toughness steel

ZHANG Xiao-feng^{1, 2
, ,},
WAN Ya-xiong^{1, 2},
WU Xue-jun^{1, 2},
KAN Zhong-wei^{1, 2},
HUANG Zhen-yi^{1, 2}

1.
Anhui Province Key Laboratory of Metallurgical Engineering and Resources Recycling (Anhui University of Technology), Maanshan 243002, China
2.
School of Metallurgical Engineering, Anhui University of Technology, Maanshan 243002, China

More Information

Corresponding author: E-mail: egzxf@ahut.edu.cn

摘要

摘要: 隨著汽車行業的快速發展，輕量化汽車用鋼的研發和應用越來越廣泛。抗拉強度超過1000 MPa的第二、三代汽車用鋼往往是復相組織，通過固溶、析出、變形、細晶強化等各種強化方式，在基體中形成大量缺陷，導致鋼材服役過程中對氫更加敏感，容易在很小的氫溶解條件下發生氫脆。Fe?Mn?C系、Fe?Mn?Al?C系等含Mn量高的汽車結構用鋼因層錯能較高，不僅直接決定了其強韌性機制，還對其服役性能有重要影響。在Fe?Mn?C系TWIP鋼的成分基礎上，添加少量Al元素，形成Fe?Mn?(Al)?C鋼，不僅能降低鋼材密度，提高鋼材的強韌性，也因Al元素改變了鋼材的微觀組織構成，一定程度上令氫脆得到緩解。但當Al含量較高時，形成低密度鋼，其組織構成更加復雜，析出物更多，導致氫脆敏感性更顯著。本文從Fe?Mn?(Al)?C高強韌性鋼的組織構成、第二相、晶體缺陷等特征出發，綜述了H在Fe?Mn?(Al)?C鋼中的滲透、溶解和擴散行為，H與基體組織、析出相、晶格缺陷的交互作用，H在鋼中的作用模型、氫脆機制、氫脆評價手段和方法等。并評述了Fe?Mn?(Al)?C高強韌性鋼氫脆問題開展的相關研究工作和最新發展動態，指出通過第一性原理計算、分子動力學模擬和借助氫原子微印技術、三維原子探針等物理實驗相結合的方法是從微觀層面揭示高強韌性鋼氫脆機制的未來發展方向。
- 低密度鋼 /
- TWIP /
- 氫脆 /
- 晶格缺陷 /
- 微觀機制
Abstract: With the rapid development of the automobile industry, the development and application of lightweight automobile steel are increasingly extensive. The second- and third-generation automobile steels with a tensile strength of over 1000 MPa are usually of duplex structure. Through solid solution strengthening, precipitation, deformation, fine grain strengthening, and other strengthening methods, a large number of defects are formed in the matrix, which makes the steel more sensitive to hydrogen in the service process and prone to hydrogen embrittlement under very small hydrogen dissolution conditions. The high-Mn content steels Fe?Mn?C and Fe?Mn?Al?C steels have high stacking fault energy, which not only influences their strength and toughness but also significantly affects their service performance. Based on the composition of twinning-induced plasticity (TWIP) steel of the Fe?Mn?C system, adding a small amount of Al element to form Fe?Mn?(Al)?C steel can not only reduce the steel density and improve the steel strength and toughness but also change the steel microstructure to a certain extent; the effect on the microstructure reduces the steel susceptibility to hydrogen embrittlement. However, when the Al content is high, low-density steel with a more complex structure is formed, and the precipitates are more, which leads to a more significant sensitivity to hydrogen embrittlement. In this paper, the permeation, dissolution, and diffusion behavior of H in Fe?Mn?(Al)?C high-strength-and-toughness-steel; the interaction between H and the matrix structure, the precipitated phase, and lattice defects; the model of H in steel; the hydrogen embrittlement mechanism; and the methods of hydrogen embrittlement evaluation were summarized based on the structure, second phase, and crystal defects of Fe?Mn?(Al)?C high-strength-and-toughness steel. The related research work and the latest developments of the hydrogen embrittlement of Fe?Mn?(Al)?C high-strength-and-toughness steel were reviewed. The development direction of the hydrogen embrittlement microstructure mechanism of high-strength-and-toughness steel was revealed by combining first-principle calculations, molecular dynamics simulation, and physical experiments such as hydrogen atom microprinting technology and three-dimensional atomic probe analysis.
- low-density steel /
- twinning-induced plasticity /
- hydrogen embrittlement /
- lattice defect /
- microstructure mechanism

HTML全文

圖 1 晶體缺陷中氫脆現象及示意圖^[14]

Figure 1. Hydrogen embrittlement phenomena and mechanisms^[14]

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圖 2 鐵的三種晶體結構^[25]。（a）面心立方結構；（b）體心立方結構；（c）密排六方結構；（d）H在八面體和四面體間隙

Figure 2. Three crystal structures of iron^[25]: (a) face-centered cubic structure; (b) body-centered cubic structure; (c) close-packed hexagonal structure; (d) diagrams of H in octahedral and tetrahedral interstices

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圖 3 氫原子在BCC、FCC和HCP晶格的遷移路徑^{[23, 28]}

Figure 3. Migration path of hydrogen atom in BCC, FCC, and HCP crystalline lattices^{[23, 28]}

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圖 4 FCC晶體中的層錯堆垛示意圖^[35-36]。（a）無限層錯；（b）兩個不全位錯為界的終止層錯

Figure 4. Schematics of stacking faults in an FCC crystal described by stacking operators^[35-36]: (a) an infinite stacking fault; (b) a terminated stacking fault bounded by two partial dislocations

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圖 5 變形孿晶界氫俘獲示意圖（TB：孿晶界）^[38]。（a）變形孿晶尖端的應力集中；（b）位錯孿晶交叉形成的臺階處的應變場；（c）偽孿晶形成引起的晶格畸變；（d）變形孿晶的納米結構，包括位錯和納米孿晶帶

Figure 5. Schematics describing the factors affecting hydrogen trapping at the deformation twin boundaries (TB: twin boundary)^[38]: (a) stress concentration at a tip of a deformation twin; (b) strain field at the steps formed by the dislocation–twin intersection; (c) lattice distortion due to pseudo-twin formation; (d) nanoscale structure of deformation twins, including dislocations and nanotwin plates

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圖 6 氫在不同位置的溶解能^[39]。（a）BCC鐵中的四面體位和BCC∑3, BCC∑5晶界內各種中間(im)和界面 (if)的間隙吸附位；（b）FCC鐵中的八面體位, FCC∑3和FCC∑11 Fe晶界內各種中間(im)和界面(if)的間隙吸附位

Figure 6. Solution energy of hydrogen as a function of the volume of the interstitial site^[39]: (a) tetrahedral sites in BCC Fe and various intermediate (im) and interface (if) interstitial adsorption sites within BCC∑3 and BCC∑5 Fe grain boundaries; (b) octahedral sites in FCC Fe and various intermediate (im) and interface (if) interstitial adsorption sites within FCC∑3, and FCC∑11 Fe grain boundaries

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圖 7 氫?金屬平衡中的能量關系及氫在不同位置的遷移示意圖

Figure 7. Schematic view of the energy relationship in hydrogen?metal equilibria and hydrogen migration in different sites

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圖 8 缺陷形成、氫偏析、孿生應力集中和開裂的順序過程示意圖^{[13, 54]}

Figure 8. Schematic of the sequential process of defect formation, hydrogen segregation, twinning-induced stress concentration, and cracking^{[13, 54]}

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圖 9 三叉晶界與變形孿晶界的裂紋起源^[38]。（a）三叉晶界；（b）變形孿晶界

Figure 9. Crack initiation from a triple junction of grain boundaries and a grain boundary intercepting deformation twinning^[38]: (a) a triple junction of the grain boundaries；(b) a grain boundary intercepting deformation twinning

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圖 10 預誘導孿晶阻礙冷軋樣品充氫后位錯滑移的示意圖

Figure 10. Graphical illustration showing the effect of preinduced twins on preventing dislocation slip after H-charging in cold-rolled sample

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圖 11 Fe?18Mn?xAl鋼的熱解吸分析（TDA）曲線和斷裂應力^{[13, 42, 58]}。（a）相同充氫條件下的TDA；（b）不同擴散氫條件下缺口試樣的斷裂應力

Figure 11. TDA profiles and fracture stress with different Al contents in Fe?18Mn?xAl steels^{[13, 42, 58]}: (a) TDA profiles at an identical hydrogen charging condition; (b) plot of fracture stress of notched specimens against diffusible hydrogen content

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圖 12 含κappa碳化物Fe?26Mn?11Al?1.2C奧氏體鋼的氫致晶間裂紋^{[13, 51]}。（a）反極圖（IPF）；（b）充氫條件下的KAM圖；（c）晶間裂紋形成

Figure 12. Hydrogen-induced intergranular crack in Fe?26Mn?11Al?1.2C austenitic steel containing κ-carbides^{[13, 51]}: (a) inverse pole figure (IPF); (b) kernel average misoritation（KAM）maps under hydrogen charging; (c) intergranular crack formation

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圖 13 氫輔助裂化混合機制的示意圖^[66]。（a）HELP與HEDE機制共同作用下的AIDE機制；（b）AIDE與HEDE機制

Figure 13. Schematics illustrating the hybrid mechanisms of hydrogen-assisted cracking^[66]: (a) AIDE with contributions from HELP and HEDE; (b) AIDE alternating with HEDE

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圖 14 鋼中氫輔助裂紋和裂紋擴展的示意圖^[51]。（a）晶界處應變局部化；（b）擴散氫沿晶界向應變局部化區域遷移；（c）應變局部化帶晶界處形成的微空洞；（d）微空洞合并及沿晶界傳播

Figure 14. Schematic sketches showing hydrogen-assisted cracking and crack propagation in the steel^[51]: (a) strain localization occurring particularly on grain boundaries; (b) diffusible hydrogen moving to the strain localization regions along the grain boundaries; (c) formation of micro-voids on the grain boundary intersecting strain localization bands; (d) micro-voids coalescence and subsequent propagation along grain boundaries

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表 1 α-Fe、γ-Fe和ε-Fe的晶格特征

Table 1. Crystallographic characteristics of α-Fe，γ-Fe, and ε-Fe structures

Type of crystal structure	Lattice constant/ nm	Atomic radius, r/ nm	Size of tetrahedral interstice/ nm	Size of octahedral interstice/ nm	Hydrogen atomic radius/ nm
FCC	a=b=c=0.344	$r = \sqrt 2 a/4 = {\rm{0}}{\rm{.}}1216$	0.225r=0.0274	0.414r=0.0503	0.037
BCC	a=b=c=0.286	$r = \sqrt 3 a/4 = {\rm{0}}{\rm{.}}1238$	0.291r=0.0360	0.154r=0.0191
HCP	a=b=0.245, c/a=0.1584	$r{\rm{ = }}a/2 = {\rm{0}}{\rm{.}}1225$	0.225r=0.0275	0.414r=0.0507

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表 2 氫在BCC、FCC、FCT和HCP中擴散的遷移能

Table 2. Migration energy of hydrogen diffusion in BCC, nonmagnetic FCC, antiferromagnetic FCT, and HCP

Type of crystal structure	Path			Migration energy/eV
Type of crystal structure	1#	2#	3#	1#	2#	3#
BCC	T₁—T₂	T₁—O—T₃	—	0.088	0.123	—
FCC(Nonmagnetic)	O₁—T—O₃	O₁—O₃	—	0.64	1.08	—
FCC(Antiferromagnetic)	O₁—T—O₃	O₁—O₃	—	0.44	0.84	—
FCT	O₁—T—O₃	O₁—O₂	O₁—O₃	0.44	0.72	1.07
HCP	O₁—O₂	O₁—T—O₃	O₁—O₃	0.72	0.77	1.26

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表 3 氫與鋼中元素、空位及陷阱位的結合能

Table 3. Elements and vacancy in steel and selected trap sites binding energy values of H in steel

Atom and vacancy defect sites	Binding energy between H atom and point defect/ eV	Trap sites	Binding energy between H atom and line, surface, volume defects/ (kJ·mol^?1)	References
H with vacancy	0.57	Substitutional Ni in Fe	7.7?9.7	[25, 48]
H with solid solution atom	0.57?0.60	Dislocation / Dislocation cores	19.2?26 / 58?(62.2±0.3)	[25, 48-50]
H with carbon atom	0.09	Grain boundaries	20?46	[25, 48-49]
H with aluminium atom	0.04	α/γ interface	?52	[25, 48]
H with copper atom	0.06	α/cementite interface	8.4?13.4	[25, 48]
H with nickel atom	0.01	Incoherent carbides	>97	[25, 48]
H with manganese and silicon atom	—	Incoherent particles in Fe	67.5?96.5	[25, 48]
		Inclusions	79	[49]
		Twin boundaries	62	[49]

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表 4 鋼中H的激活能值

Table 4. Activation energy values of H in steel

Trap site	Steel	Activation energy/(kJ·mol^?1)	References
Grain boundary	Pure iron	17	[50-51]
Elastic field of edge dislocation	Pure iron Martensitic steel Austenitic steel	27–35	[50-52]
Micro-void	Pure iron	35	[50-51]
Σ3 twin boundary	Austenitic steel	62	[51-52]
Dislocation core	Martensitic steel	58	[51, 53]
k-carbides	Austenitic steel	76–80	[51]

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表 5 BCC、FCC和HCP晶體中不同位置的氫形成能

Table 5. Formation energy of H in different sites of BCC, FCC, and HCP Fe crystal

Type of crystal structure	T-site/ eV	O-site/ eV	Formation energy of substitutional /eV	Formation energy of vacancy /eV	T-site near a single vacancy /eV	O-site near s single vacancy /eV
BCC	?3.17	—	2.61	2.44	—	?3.24
FCC	?2.68	?3.24		2.39	?3.705	?3.717
HCP	?2.79	?3.30

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表 6 晶界處氫擴散的計算數值

Table 6. Calculated values of hydrogen diffusion at grain boundaries

Grain size, d/μm	Grain boundary area per unit volume, ${S_v}$/(m²·m^?3)	Content of diffusible hydrogen, $X_{\rm{H}}^{{\rm{all}}}$/10^?6	Hydrogen mass per unit grain boundary area, $Y_{\rm{H}}^{{\rm{GB}}}$ /(g·m^?2)
37	5.4×10⁴	3.30	4.8×10^?4
2.3	8.7×10⁵	4.58	4.1×10^?5
0.85	2.4×10⁶	7.10	2.4×10^?5

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