硫对镍基合金825(100)电子结构影响的密度泛函研究
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摘要
由于硫在镍基合金表面易产生点蚀,基于密度泛函理论,利用软件对镍基合金825表面吸附元素硫进行了计算,研究了硫对合金表面电子结构及耐蚀性的影响。研究表明,S在合金825面心立方晶胞(100)Ni/Fe终止面上的H位吸附能达到-6.51 eV,相互作用较强且稳定吸附;S在合金(100)面的吸附主要是由S-3p轨道与Fe-3d轨道以及第二层Cr-3d轨道杂化引起;综合分析电子态密度、电荷布居、差分电荷密度,硫在合金(100)面吸附后电子态呈扩散趋势,活性增加,带负电,Ni-S间的弱耦合作用阻碍了Fe-S成键,Ni的存在提高了合金的耐蚀性;当S覆盖度从0.25ML升高到1.0ML时,在0.5ML附近S与合金的相互作用达到极大,在1.0ML附近时相邻S原子间的耦合和杂化阻碍了S在(100)面上的吸附。
The local accumulation of sulfur adsorbed on the pipeline will make local corrosion occur, in order to reveal the corrosion mechanism, DFT was used to calculate and analyze the atomic S adsorption on Ni-based 825 alloy(100) surface. The results show that the most favourable adsorption site for atomic S on the 825 alloy(100) surface is the H position on the Ni/Fe-terminated surface. When the coverage of S increases to a certain extent, the S-S bond coupling and hybridization hinder the adsorption of atomic S on the 825 alloy(100) surface. From the PDOS and the charge density difference, it's obvious that the interaction of the atomic S and the 825 alloy(100) surface is mainly contributed to the S-3 p, the Cr-3 d and the Fe-3 d state. Altuough orbital coupling and hybridization between Ni and S is not strong, Ni is the important factor to inhibit the S adsorption on the 825 alloy. When the S coverage increased from 0.25 ML to 1.0 ML, the interaction of S with the alloy in the vicinity of 0.5 ML reached a maximum, and the coupling and hybridization between the adjacent S atoms in the vicinity of 1.0 ML hindered the adsorption of S on the(100) surface.
The local accumulation of sulfur adsorbed on the pipeline will make local corrosion occur, in order to reveal the corrosion mechanism, DFT was used to calculate and analyze the atomic S adsorption on Ni-based 825 alloy(100) surface. The results show that the most favourable adsorption site for atomic S on the 825 alloy(100) surface is the H position on the Ni/Fe-terminated surface. When the coverage of S increases to a certain extent, the S-S bond coupling and hybridization hinder the adsorption of atomic S on the 825 alloy(100) surface. From the PDOS and the charge density difference, it's obvious that the interaction of the atomic S and the 825 alloy(100) surface is mainly contributed to the S-3 p, the Cr-3 d and the Fe-3 d state. Altuough orbital coupling and hybridization between Ni and S is not strong, Ni is the important factor to inhibit the S adsorption on the 825 alloy. When the S coverage increased from 0.25 ML to 1.0 ML, the interaction of S with the alloy in the vicinity of 0.5 ML reached a maximum, and the coupling and hybridization between the adjacent S atoms in the vicinity of 1.0 ML hindered the adsorption of S on the(100) surface.
引文
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4 Jin P,Robbins W K,Bota G.Energy & Fuels,2017,31(9),10222.
5 Alfonso D R.Surface Science,2008,602(16),2758.
6 刘智勇,董超芳,李晓刚,等.北京科技大学学报,2009,31(3),318.
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12 张杨,黄燕,陈效双,等.物理学报,2013,62(20),206102.
13 Pan Y ,Guan W .International Journal of Hydrogen Energy,2016,41(26),11033.
14 栾扬,赵志曼,全思臣,等.材料导报:研究篇,2018,32(6),2118.
15 戈磊,陈长风,郑树启,等.腐蚀与防护,2009(10),708.
16 蔡晓文,戈磊,于浩波,等.材料科学与工程学报,2010,28(2),226.
17 Yunhai Bai,Demetrios Kirvassilis,Lang Xu,et al.Surface Science,2019,67(9),240.
18 Hernandez J M,Lim D H,Nguyen H V P,et al.International Journal of Hydrogen Energy,2014,39(23),12251.
19 Gallegos M D,et al.Journal of Physics:Condensed Matter,2002,14(11),2717.
20 Carlo M,Councilman V,et al.Physical Review B,2000,62(4),2899.
21 David Vanderbilt.Physical Review:B Condensed Matter,1990,4111,7892.
22 Guo J,Geng Z,Dong J,et al.Rare Metal Materials & Engineering,2012,41(11),1929.
23 Wen P,Li C F,Chaos Y,et al.Acta Physic Silica,2014,6319,809.
24 黄俊,李荣兴,谢刚,等.材料导报:研究篇,2018,32(10),39.
25 罗强,张智,唐斌,等.原子与分子物理学报,2012,29(4),364.
26 o?tys J,Piechota J,Strak P,et al.Applied Surface Science,2017,393(2),168.