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为了从微观结构层次进一步深入研究和完善预应变/预应力与H吸附钢（Fe-C合金）表面的作用机制,采用第一性原理的方法计算了单轴预应变对C掺杂Fe（110）表面的H吸附、扩散的影响，从表面原子空间构型、结合能(Eb)、电子结构三个方面探究了预应变对H吸附、渗透的影响，并计算了掺杂和未掺杂C原子时H渗透的扩散能垒。结果表明，掺杂的C原子使Fe晶体的八面体空间在不同方向上发生畸变，从而使Fe（110）表面产生了“畸变”，不同位点处畸变程度（D∆）和离C原子本身的距离不一致，导致各位点在预应变下的吸附结构（H吸附高度d和单元表面积S∆）与结合能（Eb）变化趋势不一致，扩散能垒变化趋势与结合能变化趋势相反。研究发现，H吸附在C掺杂位点时，吸附结构和结合能计算结果显示H有更容易扩散到内部中的趋势，而电子结构计算结果显示C原子与H原子相斥，扩散能垒相较于未掺杂时升高，H原子难以扩散进入体相内部而在C周围富集，继而诱发氢脆。吸附结构、结合能、扩散能垒计算结果显示:在掺杂位点（TFS位点）处，随着拉伸应变增大，H原子越容易扩散到钢的微观结构中，随着压缩应变增大，H原子越难扩散到钢的微观结构中，可利用压缩应变减小钢中氢脆的发生。这从微观层面解释了实际工程应用中“同等应力情况下，C越多，钢铁发生氢脆的倾向越严重”的原因，从电子结构层次完善了预应变下H吸附钢（Fe-C合金）表面的作用机制，可对氢脆的研究提供参考。To further investigate and refine the mechanism of pre-strain/pre-stress interaction with hydrogen adsorption on steel (Fe-C alloy) surfaces at the microstructural level, first-principles calculations were employed to study the effects of uniaxial pre-strain on hydrogen adsorption and diffusion at C-doped Fe(110) surfaces. The influence of pre-strain on hydrogen adsorption and permeation was explored through three aspects: atomic spatial configuration, binding energy (Eb), and electronic structure, while diffusion energy barriers for hydrogen permeation were calculated with and without C atom doping. Results demonstrate that doped C atoms induce octahedral lattice distortion in Fe crystals across different directions, creating "distortion" on the Fe(110) surface. Variations in distortion degree (DΔ) at different sites and their distances from C atom lead to inconsistent trends in adsorption configurations (H adsorption height d and unit surface area SΔ) and binding energy (Eb) under pre-strain. For adsorption configurations, d is coupled by ε and C atom effects: at the TFpure site (non-C-doped site ), d decreases as SΔ increases; under compression(ε decreases from 0% to -5%) at TF (C-doped site with C atom directly beneath the site), TFs (C-doped site located closer to the maximally distorted atom Fe135) and TFL sites (C-doped site located farther from the maximally distorted atom Fe135), d positively correlates with DΔ, while under tension (ε increases from 0% to 5%), d negatively correlates with SΔ. For Eb, as ε increases from -5% to 5%, Eb at TFpure peaks then declines, whereas Eb at TF decreases initially before rising, and Eb at TFS/TFL monotonically increases. Analysis reveals that Eb at TFS/TFL positively correlates with the standard deviation (Sα) of the three internal angles in the triangular unit. The diffusion energy barrier (E∆) trends inversely with Eb. When H adsorbs at C-doped sites, adsorption configuration and binding energy calculations suggest H tends to diffuse inward more readily. However, electronic structure analysis reveals repulsion between C and H atoms, accompanied by increased diffusion barriers compared to undoped cases, causing H atoms to accumulate around C atoms rather than penetrating the bulk phase, thereby inducing hydrogen embrittlement. Adsorption configuration, binding energy, and diffusion barrier calculations indicate that at doped sites (TFS site), increasing tensile strain facilitates H diffusion into the steel microstructure, whereas compressive strain hinders it. This explains the engineering phenomenon where "higher carbon content exacerbates hydrogen embrittlement tendency under equivalent stress" at the atomic scale. The study elucidates the mechanism of H adsorption on pre-strained Fe-C alloy surfaces from an electronic structure perspective, providing theoretical insights for hydrogen embrittlement research.
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Keywords:
- First principles /
- α-Fe(C) /
- Pre-strain /
- H adsorption
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