陈敬昶,张慧蒙,符荣,刘学渊,王远.In掺杂促进AuCuNi合金表面氧化膜形成的第一性原理计算[J].表面技术,2022,51(12):101-108.
CHEN Jing-chang,ZHANG Hui-meng,FU Rong,LIU Xue-yuan,WANG Yuan.First-principles Calculation of Promoting the Formation of Oxide Film on AuCuNi Alloy Surface by In Doping[J].Surface Technology,2022,51(12):101-108 |
| In掺杂促进AuCuNi合金表面氧化膜形成的第一性原理计算 |
| First-principles Calculation of Promoting the Formation of Oxide Film on AuCuNi Alloy Surface by In Doping |
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| DOI：10.16490/j.cnki.issn.1001-3660.2022.12.009 |
| 中文关键词: 金基合金 氧化膜 第一性原理计算 吸附特性 掺杂形成能 |
| 英文关键词:gold-base alloy oxide film first-principles calculation adsorption characteristics doping formation energy |
| 基金项目:云南省农业基础研究联合专项基金(2018FG001-062);国家自然科学基金(51301144);云南省教育厅科学研究基金项目(2022J0500) |
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| Author | Institution |
| CHEN Jing-chang | School of Mechanical Engineering and Transportation, Southwest Forestry University, Kunming 650224, China |
| ZHANG Hui-meng | School of Mechanical Engineering and Transportation, Southwest Forestry University, Kunming 650224, China |
| FU Rong | School of Mechanical Engineering and Transportation, Southwest Forestry University, Kunming 650224, China |
| LIU Xue-yuan | School of Mechanical Engineering and Transportation, Southwest Forestry University, Kunming 650224, China |
| WANG Yuan | School of Mechanical Engineering and Transportation, Southwest Forestry University, Kunming 650224, China |
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| 中文摘要: |
| 目的 采用第一性原理计算In掺杂促进AuCuNi合金表面氧化膜的形成机制，以为在金基合金中掺杂元素，促进表面氧化膜生成提供理论依据。方法 基于构建适用于第一性原理计算、原子比Au:Cu:Ni=9:5:2的晶体结构模型，对In掺杂AuCuNi体系模型的稳定性、偏析特性以及吸附特性进行计算。结果 In原子替代掺杂AuCuNi合金(111)面中各元素后形成新的AuCuNiIn表面，掺杂形成能均为负值，这说明In替位AuCuNi合金(111)面中任何一个原子都会促进AuCuNi表面的稳定性。当In替位掺杂AuCuNi表面第一层的Ni原子时，稳定性提升最大，掺杂形成能为–1.326 eV;当In替位掺杂AuCuNi表面第三层的Ni原子时，掺杂形成能最大为‒0.503 eV，这表明当In原子掺杂到该位置时，体系稳定性的提升最小。通过偏析能的计算发现，掺杂后的In有向其他位点偏析的趋势，最易向偏析能最小的位点偏析，即向表层Ni原子偏析，偏析能为‒0.739 eV。因此，使In原子替位掺杂第一层的Ni原子，形成最稳定的AuCuNiIn表面结构。此外，通过在AuCuNiIn表面吸附氧原子和计算吸附能发现，当原子顶位吸附时吸附能都比较高，这说明Au、Cu、Ni原子都不易在顶位吸附氧原子，其中T3(Au)位点的吸附能为0.034 eV，其值大于0，说明Au原子的顶位不会自发地吸附氧原子。表层原子中吸附能最低的几个位点H3(‒3.571 eV)、H1(‒3.462 eV)、B2(‒3.021 eV)的氧原子均与In原子成键，这说明In原子附近更易吸附氧原子。最后，通过电荷差分密度图和布居分析，发现O原子与周围其他原子有明显的电荷转移，并与In原子、Cu原子和Ni原子形成键。这进一步表明O原子与周围原子发生化学反应，提高了材料表面的稳定性，证实了吸附能计算的准确性。结论 基于以上计算分析得出In原子的掺杂可以有效促进AuCuNi表面氧化膜的形成。通过第一性原理计算预测了元素掺杂对材料表面性能的影响，为掺杂促进材料表面氧化膜的形成提供了一定的理论参考。 |
| 英文摘要: |
| Au is difficultly satisfied with work in the extreme environments such as high friction, high wear and strong corrosion due to it hardly reacts with oxygen to form a dense oxide film. Therefore, the formation mechanism of In doping in AuCuNi alloy to form the surface oxide film was calculated by First-principles in order to provide a theoretical basis for promoting the formation of surface oxide film by doping elements in the Au-based alloy in this paper. A crystal structure model with Au:Cu:Ni=9:5:2 suitable for First-principles calculations was constructed to calculate the stability, bias properties and adsorption properties of AuCuNi system with In doping. The results show:the doping formation energies of all new forming AuCuNiIn surfaces with In doping substitution for each element in AuCuNi (111) face are negative, this indicates that the stability of the AuCuNi surface can be promote by In substitution for any element in the AuCuNi (111) face, and when In substitution Ni atom in the first layer on AuCuNi surface, the greatest stability enhancement occurs with a doping formation energy of ‒1.326 eV. The maximum doping formation energy is ‒0.503 eV when In atoms substituting for Ni atoms in the third layer, which indicates that the increasing of the stability of the system is minimum at In atoms locating on the site. The bias energy calculation indicates that the doped In has a tendency to bias towards other sites and most easily towards the site of Ni atom with the lowest bias energy with value of ‒0.739 eV so the most stable AuCuNiIn surface structure is obtained when In substitute for a Ni atoms on the first layer. In addition, it is found that the adsorption energies are relatively high when In is adsorbed in the top position by the calculation of the adsorption energies, this indicated that Au, Cu and Ni atoms aren’t prone to adsorbing oxygen atoms in the top position, as well as the adsorption energy at T3 (Au) site is positive with value of 0.034 eV to explain Au on the top site don’t spontaneously adsorb oxygen atoms. All the oxygen atoms at the lowest adsorption energies in the surface atoms, H3 (‒3.571 eV), H1 (‒3.462 eV) and B2 (‒3.021 eV) are bonded to In atom to suggest that oxygen atom is more readily adsorbed near In atoms. Finally, it is found that O atom obviously transfers charge with the other surrounding atoms, and forms bonds with In, Cu and Ni atom by the charge differential density map and population analysis, i.e., a chemical reaction occurs between the O atom and the surrounding atoms, which improves the stability of the material and confirms the accuracy of the adsorption energy calculation. Based on the above calculation and analysis, it is concluded that the formation of oxide films on the AuCuNi surface can be effectively promote by In doping. In addition, the effects of doping element on surface properties were predicted by first-principles calculations, which provided a certain theoretical reference for promoting the formation of oxide films by doping element in the surface of materials in this paper. |
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