应变与合金元素对空位氢陷阱作用的影响

黄璞; 成林; 许泽岷; 夏锴; 胡丞杨; 吴开明

doi:10.3969/j.issn.1674-6457.2026.01.022

PDF(6797 KB)

精密成形工程 ›› 2026, Vol. 18 ›› Issue (1) : 236-247. DOI: 10.3969/j.issn.1674-6457.2026.01.022

钢铁成形

应变与合金元素对空位氢陷阱作用的影响

黄璞^a, 成林^a,b,*, 许泽岷^b, 夏锴^b, 胡丞杨^b, 吴开明^a,b

作者信息 +

Effect of Strain and Alloying Elements on Hydrogen Trapping of Vacancy

HUANG Pu^a, CHENG Lin^a,b,*, XU Zemin^b, XIA Kai^b, HU Chengyang^b, WU Kaiming^a,b

Author information +

文章历史 +

摘要

目的揭示应变、置换型合金元素及间隙型合金元素对体心立方（BCC）铁中空位氢陷阱效应的影响机制,为提高钢材的抗氢脆性能提供理论支持。方法基于密度泛函的第一性原理计算方法,系统研究了单轴应变及不同类型合金元素对BCC铁中空位的氢陷阱的结合能影响,计算分析了结构的电子密度分布和态密度。结果单轴应变可以降低空位形成能,并对氢-空位结合能的影响呈现强烈的各向异性：垂直于应变轴的空位氢陷阱能力下降,而平行于应变轴的空位氢陷阱能力增强。此外,置换型合金元素（Mn、Si、Cr、Mo、Ti、W、Li、Al、Cu、Ni、Co、V）可通过调控局部电子结构和晶格畸变,在不同取向上分别削弱或增强氢的陷阱作用;间隙型合金元素（C、N）则通过引发显著的晶格畸变和电子结构重排,在空位周围形成2个稳定的氢捕获位点。结论揭示了应变及合金元素对BCC铁中空位氢陷阱效应的微观机制,发现应变诱导的晶格畸变对氢陷阱能力具有方向性影响,而合金元素的体积参数和电子结构调控作用对氢-空位相互作用起决定性作用。这些结果为优化合金设计、提高钢材抗氢脆能力提供了重要的理论依据。

Abstract

The work aims to elucidate the mechanisms by which strain, substitutional alloying elements, and interstitial alloying elements affect hydrogen trapping at vacancies in body-centered cubic (BCC) iron, thereby providing theoretical guidance for enhancing hydrogen embrittlement resistance in steels. Based on first-principles calculations within the framework of density functional theory, the effects of uniaxial strain and various alloying elements on the binding energy of hydrogen-vacancy complexes in BCC iron were systematically investigated and the electronic charge density distributions and density of states were calculated and analyzed. The uniaxial strain reduced the vacancy formation energy and induced a pronounced anisotropy in hydrogen trapping behavior: hydrogen binding energy at vacancies aligned parallel to the strain axis was enhanced, while it was weakened in directions perpendicular to the axis. Substitutional alloying elements (Mn, Si, Cr, Mo, Ti, W, Li, Al, Cu, Ni, Co, and V) modulated the local electronic structure and lattice distortion, leading to orientation-dependent enhancement or suppression of hydrogen trapping. Interstitial elements (C and N) caused significant lattice distortion and electronic redistribution, generating two energetically favorable hydrogen trapping sites around the vacancy. These results uncover the microscopic mechanisms by which strain and alloying elements affect hydrogen-vacancy interactions in BCC iron. Strain-induced lattice distortion exhibits directional control over hydrogen trapping capacity, while the atomic size and electronic characteristics of alloying elements play a decisive role in modulating hydrogen-vacancy binding. These results provide essential theoretical insights for the design of advanced alloys with improved resistance to hydrogen embrittlement.

导出引用

黄璞, 成林, 许泽岷, 夏锴, 胡丞杨, 吴开明. 应变与合金元素对空位氢陷阱作用的影响[J]. 精密成形工程. 2026, 18(1): 236-247 https://doi.org/10.3969/j.issn.1674-6457.2026.01.022

HUANG Pu, CHENG Lin, XU Zemin, XIA Kai, HU Chengyang, WU Kaiming. Effect of Strain and Alloying Elements on Hydrogen Trapping of Vacancy[J]. Journal of Netshape Forming Engineering. 2026, 18(1): 236-247 https://doi.org/10.3969/j.issn.1674-6457.2026.01.022

中图分类号： O474

参考文献

[1] CHIARI L, NOZAKI A, KOIZUMI K, et al.Strain-Rate Dependence of Hydrogen-Induced Defects in Pure α-Iron by Positron Annihilation Lifetime Spectroscopy[J]. Materials Science and Engineering: A, 2021, 800: 140281.
[2] FUKUNAGA A.Effect of High-Pressure Hydrogen Environment in Elastic and Plastic Deformation Regions on Slow Strain Rate Tensile Tests for Iron-Based Superalloy A286[J]. International Journal of Hydrogen Energy, 2023, 48(47): 18116-18128.
[3] FUKUNAGA A.Differences between Internal and External Hydrogen Effects on Slow Strain Rate Tensile Test of Iron-Based Superalloy A286[J]. International Journal of Hydrogen Energy, 2022, 47(4): 2723-2734.
[4] SATO K, HIROSAKO A, ISHIBASHI K, et al.Quantitative Evaluation of Hydrogen Atoms Trapped at Single Vacancies in Tungsten Using Positron Annihilation Lifetime Measurements: Experiments and Theoretical Calculations[J]. Journal of Nuclear Materials, 2017, 496: 9-17.
[5] BORONSKI E, NIEMINEN R M.Electron-Positron Density-Functional Theory[J]. Physical Review B, 1986, 34(6): 3820-3831.
[6] COUNTS W A, WOLVERTON C, GIBALA R.First-Principles Energetics of Hydrogen Traps in α-Fe: Point Defects[J]. Acta Materialia, 2010, 58(14): 4730-4741.
[7] HAYWARD E, FU C C.Interplay between Hydrogen and Vacancies in α-Fe[J]. Physical Review B, 2013, 87(17): 174103.
[8] KAWAKAMI K, MATSUMIYA T.Numerical Analysis of Hydrogen Trap State by TiC and V4C3 in BCC-Fe[J]. ISIJ International, 2012, 52(9): 1693-1697.
[9] LE PAGE Y, SAXE P.Symmetry-General Least-Squares Extraction of Elastic Data for Strained Materials From ab Initio Calculations of Stress[J]. Physical Review B, 2002, 65(10): 104104.
[10] SAKAKI K, KAWASE T, HIRATO M, et al.The Effect of Hydrogen on Vacancy Generation in Iron by Plastic Deformation[J]. Scripta Materialia, 2006, 55(11): 1031-1034.
[11] LI S-Y, WANG Y, ZHAO W-M.Influence of Single Axis Strain on Site Occupation and Diffusion of Hydrogen Atom in α-Fe[J]. Acta Physica Sinica, 2017, 66(18): 187101.
[12] YOU Y, YAN M F.Interactions of Foreign Interstitial and Substitutional Atoms in Bcc Iron from Ab Initio Calculations[J]. Physica B: Condensed Matter, 2013, 417: 57-69.
[13] SUGIMOTO H, FUKAI Y.Hydrogen-Induced Superabundant Vacancy Formation in Bcc Fe: Monte Carlo Simulation[J]. Acta Materialia, 2014, 67: 418-429.
[14] NAGUMO M, TAKAI K.The Predominant Role of Strain-Induced Vacancies in Hydrogen Embrittlement of Steels: Overview[J]. Acta Materialia, 2019, 165: 722-733.
[15] POLFUS J M, LØVVIK O M, BREDESEN R, et al. Hydrogen Induced Vacancy Clustering and Void Formation Mechanisms at Grain Boundaries in Palladium[J]. Acta Materialia, 2020, 195: 708-719.
[16] SUGITA K, MUTOU Y, SHIRAI Y.Vacancy Clustering Behavior in Hydrogen-Charged Martensitic Steel AISI 410 under Tensile Deformation[J]. Journal of Physics: Conference Series, 2016, 674(1): 012006.
[17] TSUCHIDA Y.Lattice Defects Revealed by Hydrogen Thermal Desorption Analysis of Carbon Steel Strained with/without Hydrogen Pre-Charging[J]. ISIJ International, 2014, 54(4): 963-969.
[18] TATEYAMA Y, OHNO T.Stability and Clusterization of Hydrogen-Vacancy Complexes in α-Fe: An Ab Initio Study[J]. Physical Review B, 2003, 67(17): 174105.
[19] HAYWARD E, DEO C, UBERUAGA B P, et al.The Interaction of a Screw Dislocation with Point Defects in Bcc Iron[J]. Philosophical Magazine, 2012, 92(22): 2759-2778.
[20] OHSAWA K, EGUCHI K, WATANABE H, et al.Configuration and Binding Energy of Multiple Hydrogen Atoms Trapped in Monovacancy in Bcc Transition Metals[J]. Physical Review B, 2012, 85(9): 094102.
[21] GUOCAI L, ZHANG M, ZHANG H, et al.Hydrogen Diffusion and Vacancy Clusterization in Iron[J]. International Journal of Hydrogen Energy, 2018, 43(32): 15378-15385.
[22] SMIRNOVA D, STARIKOV S.Atomistic Study of Hydrogen Diffusion in Presence of Defects in Bcc and Fcc Iron[J]. Computational Materials Science, 2023, 230: 112433.
[23] HIRAYAMA S, SATO K, KATO D, et al.Effect of Uniaxial Tensile Strain on Binding Energy of Hydrogen Atoms to Vacancy-Carbon-Hydrogen Complexes in α-Iron[J]. Nuclear Materials and Energy, 2022, 31: 101179.
[24] PSIACHOS D.Ab Initio Parametrized Model of Strain-Dependent Solubility of H in α-Iron[J]. Modelling and Simulation in Materials Science and Engineering, 2012, 20(3): 035011.
[25] PSIACHOS D, HAMMERSCHMIDT T, DRAUTZ R.Ab Initio Study of the Modification of Elastic Properties of α-Iron by Hydrostatic Strain and by Hydrogen Interstitials[J]. Acta Materialia, 2011, 59(11): 4255-4263.
[26] MA Y, SHI Y F, WANG H Y, et al.A First-Principles Study on the Hydrogen Trap Characteristics of Coherent Nano-Precipitates in α-Fe[J]. International Journal of Hydrogen Energy, 2020, 45(51): 27941-27949.
[27] HOU J, KONG X S, LIU C S, et al.Hydrogen Clustering in Bcc Metals: Atomic Origin and Strong Stress Anisotropy[J]. Acta Materialia, 2020, 201: 23-35.
[28] KOMATSU A, FUJINAMI M, HATANO M, et al.Straining-Temperature Dependence of Vacancy Behavior in Hydrogen-Charged Austenitic Stainless Steel 316L[J]. International Journal of Hydrogen Energy, 2021, 46(9): 6960-6969.
[29] ZHAO H, CHAKRABORTY P, PONGE D, et al.Hydrogen Trapping and Embrittlement in High-Strength Al Alloys[J]. Nature, 2022, 602(7897): 437-441.
[30] MONASTERIO P R, LAU T T, YIP S, et al.Hydrogen-Vacancy Interactions in Fe-C Alloys[J]. Physical Review Letters, 2009, 103(8): 085501.
[31] CHENG L, LI L, ZHANG X, et al.Numerical Simulation of Hydrogen Permeation in Steels[J]. Electrochimica Acta, 2018, 270: 77-86.
[32] CHENG L, YANG B S, WU Y J, et al.Experimental and Numerical Analysis of Hydrogen Diffusion Behaviors in an Ultra-Fine Bainitic Steel[J]. International Journal of Hydrogen Energy, 2020, 45(46): 25493-25508.
[33] SAGAR S, SLUITER M H F, DEY P. First - Principles Study of Hydrogen-Carbide Interaction in Bcc Fe[J]. International Journal of Hydrogen Energy, 2024, 50: 211-223.
[34] 刘杰慧, 鲜勇, 刘政, 等. Fe和C元素对铜合金组织结构及力学性能的影响[J]. 精密成形工程, 2021, 13(5): 141-146.
LIU J H, XIAN Y, LIU Z, et al.Effects of Fe and C on the Structure and Mechanical Properties of Copper Alloys[J]. Journal of Netshape Forming Engineering, 2021, 13(5): 141-146.
[35] KRESSE G, FURTHMÜLLER J. Efficiency of Ab-Initio Total Energy Calculations for Metals and Semiconductors Using a Plane-Wave Basis Set[J]. Computational Materials Science, 1996, 6(1): 15-50.
[36] KRESSE G, FURTHMÜLLER J. Efficient Iterative Schemes for Ab Initio Total-Energy Calculations Using a Plane-Wave Basis Set[J]. Physical Review B, 1996, 54(16): 11169-11186.
[37] KRESSE G, JOUBERT D.From Ultrasoft Pseudopotentials to the Projector Augmented-Wave Method[J]. Physical Review B, 1999, 59(3): 1758-1775.
[38] MATSUKAWA Y, YASUNAGA K, KOMATSU M, et al.Dynamic Observation of Dislocation-Free Plastic Deformation in Gold Thin Foils[J]. Materials Science and Engineering: A, 2003, 350(1/2): 8-16.
[39] HIRTH J P.Effects of Hydrogen on the Properties of Iron and Steel[J]. Metallurgical Transactions A, 1980, 11(6): 861-890.
[40] OUYANG C Y, LEE Y S.Hydrogen-Induced Interactions in Vanadium from First-Principles Calculations[J]. Physical Review B, 2011, 83(4): 045111.
[41] JIANG D E, CARTER E A.Diffusion of Interstitial Hydrogen into and through Bcc Fe from First Principles[J]. Physical Review B, 2004, 70(6): 064102.
[42] MIRZAEV D A, MIRZOEV A A, OKISHEV K Y, et al.Hydrogen-Vacancy Interaction in Bcc Iron: Ab Initio Calculations and Thermodynamics[J]. Molecular Physics, 2014, 112(13): 1745-1754.
[43] LUO F P, LIU Q Y, HUANG J, et al.Effects of Lattice Strain on Hydrogen Diffusion, Trapping and Escape in Bcc Iron from Ab-Initio Calculations[J]. International Journal of Hydrogen Energy, 2023, 48(22): 8198-8215.
[44] CONNOLLY M, MARTIN M, BRADLEY P, et al.In Situ High Energy X-Ray Diffraction Measurement of Strain and Dislocation Density Ahead of Crack Tips Grown in Hydrogen[J]. Acta Materialia, 2019, 180: 272-286.
[45] IWAMOTO M, FUKAI Y.Superabundant Vacancy Formation in Iron under High Hydrogen Pressures: Thermal Desorption Spectroscopy[J]. Materials Transactions, JIM, 1999, 40(7): 606-611.
[46] SAWADA H, OMURA T.Interaction between Hydrogen and Solute Atoms in Bcc Iron[J]. Computational Materials Science, 2021, 198: 110652.
[47] ROBERTSON I M, SOFRONIS P, NAGAO A, et al.Hydrogen Embrittlement Understood[J]. Metallurgical and Materials Transactions B, 2015, 46(3): 1085-1103.
[48] NAGAO A, DADFARNIA M, SOMERDAY B P, et al.Hydrogen-Enhanced-Plasticity Mediated Decohesion for Hydrogen-Induced Intergranular and “Quasi-Cleavage” Fracture of Lath Martensitic Steels[J]. Journal of the Mechanics and Physics of Solids, 2018, 112: 403-430.
[49] MIRZAEV D A, MIRZOEV A A, OKISHEV K Y, et al.Formation of Hydrogen-Vacancy Complexes in Alpha Iron[J]. The Physics of Metals and Metallography, 2012, 113(10): 923-926.
[50] FUKAI Y, ŌKUMA N.Evidence of Copious Vacancy Formation in Ni and Pd under a High Hydrogen Pressure[J]. Japanese Journal of Applied Physics, 1993, 32(9A): L1256.
[51] DONG L S, WANG S Z, WU G L, et al.Application of Atomic Simulation for Studying Hydrogen Embrittlement Phenomena and Mechanism in Iron-Based Alloys[J]. International Journal of Hydrogen Energy, 2022, 47(46): 20288-20309.
[52] CHEN Y S, HUANG C, LIU P Y, et al.Hydrogen Trapping and Embrittlement in Metals-A Review[J]. International Journal of Hydrogen Energy, 2025, 136(000): 789-821.
[53] KORLAPATI N V S, KHAN F, VADDIRAJU S, et al. Hydrogen Diffusion Dynamics on Fe (100) Surface: A Mechanism of Hydrogen-Induced Failure[J]. International Journal of Hydrogen Energy, 2024, 65: 177-185.