B添加对MoSi2 基化合物抗氧化性能影响的第一性原理研究

doi:10.11902/1005.4537.2024.233

中国腐蚀与防护学报

2025, Vol. 45

Issue (1): 224-230 CSTR: 32134.14.1005.4537.2024.233 DOI: 10.11902/1005.4537.2024.233

研究报告

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B添加对MoSi₂ 基化合物抗氧化性能影响的第一性原理研究

陈郑¹, 宇文佩²(

), 温思涵², 李美凤², 沙江波², 周春根²

1 郑州航空工业管理学院航空发动机学院郑州 450046
2 北京航空航天大学材料科学与工程学院北京 100191

First Principles Study on Effect of B Addition on Oxidation Resistance of MoSi₂-based Compound

CHEN Zheng¹, YUWEN Pei²(

), WEN Sihan², LI Meifeng², SHA Jiangbo², ZHOU Chungen²

1 School of Aero Engine, Zhengzhou University of Aeronautics, Zhengzhou 450046, China
2 School of Materials Science and Engineering, Beihang University, Beijing 100191, China

引用本文:

陈郑, 宇文佩, 温思涵, 李美凤, 沙江波, 周春根. B添加对MoSi₂ 基化合物抗氧化性能影响的第一性原理研究[J]. 中国腐蚀与防护学报, 2025, 45(1): 224-230.
Zheng CHEN, Pei YUWEN, Sihan WEN, Meifeng LI, Jiangbo SHA, Chungen ZHOU. First Principles Study on Effect of B Addition on Oxidation Resistance of MoSi₂-based Compound[J]. Journal of Chinese Society for Corrosion and protection, 2025, 45(1): 224-230.

全文: PDF(8111 KB) HTML

摘要:

基于第一性原理计算方法探讨了B添加对化合物偶MoSi₂/MoB氧化行为的影响。结果表明，初始氧化阶段MoSi₂/MoB两化合物界面处和MoB相具有较低的氧的吸附能、氧通过MoSi₂/MoB两化合物界面的扩散激活能较低，导致化合物表面更容易发生快速氧化，有利于保护性氧化膜的快速形成；当氧化过程达到稳定阶段时，化合物表面含有6%B (原子分数)的硼硅酸盐具有最低的氧扩散系数，具有更好的抗氧化性能。因而，精确控制B掺杂量是设计抗氧化的MoSi₂基化合物Mo-Si-B的有效策略。

关键词 ： Mo-Si-B, MoSi₂/MoB, 硼硅酸盐, 第一性原理计算

Abstract：

Based on the first-principles calculation method, the influence of B addition on the oxidation behavior of compound pair MoSi₂/MoB was comprehensively investigated. The results showed that the oxygen adsorption energy at the interface of compound pair MoSi₂/MoB, and of the compound MoB itself is lower and the diffusion activation energy of oxygen atom passing through the interface MoSi₂/MoB is also lower, which may facilitate the rapid oxidation of the compound surface during the initial oxidation stage and enable the rapid formation of a protective oxide scale. When the oxidation process reached a stable state, a scale of borosilicate with 6%B (atomic fraction) may form on the compound surface with the lowest oxygen diffusion coefficient, namely, excellent oxidation resistance of the oxide scale. Therefore, precise control of B-doping is a promising strategy for designing MoSi₂-based compound Mo-Si-B of high oxidation resistance.

Key words： Mo-Si-B MoSi₂/MoB borosilicate first-principle calculation

收稿日期: 2024-07-30 32134.14.1005.4537.2024.233

ZTFLH:

TG174.445

基金资助:国家自然科学基金(51431003);国家自然科学基金联合基金(U1435201)

通讯作者: 宇文佩，E-mail：ywp1991@buaa.edu.cn，研究方向高温合金腐蚀与防护

Corresponding author: YUWEN Pei, E-mail: ywp1991@buaa.edu.cn

作者简介: 陈郑，男，1993年生，博士生

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图1 模拟的不同材料原子结构模型

图2 计算氧吸附能的MoSi2/MoB模型

表1 几个吸附位点的氧吸附能

图3 计算氧扩散激活能的MoSi2/MoB模型

图4 氧沿不同途径扩散到化合物中相应的扩散激活能

图5 MoSi2被无定形SiO2 (0%B)及不同B含量的硼硅酸盐覆盖的模型

表2 O、Si和B在不同 B含量的硼硅酸盐中的扩散系数 (m2/s)

表3 不同B含量的硼硅酸盐的形成焓Hformation和内聚能Ecohesive

图6 Mo-Si-B化合物1250 ℃静态氧化动力学曲线

1	Murayama Y, Hanada S. High temperature strength, fracture toughness and oxidation resistance of Nb-Si-Al-Ti multiphase alloys [J]. Sci. Technol. Adv. Mater., 2002, 3: 145
2	Subramanian P R, Mendiratta M G, Dimiduk D M, et al. Advanced intermetallic alloys-beyond gamma titanium aluminides [J]. Mater. Sci. Eng., 1997, 239-240A: 1
3	Guo X P, Gao L M, Guan P, et al. Microstructure and mechanical properties of an advanced niobium based ultrahigh temperature alloy [J]. Mater. Sci. Forum, 2007, 539-543: 3690
4	Voglewede B, Rangel V R, Varma S K. The effects of uncommon silicides on the oxidation behavior of alloys from the Nb-Cr-Si system [J]. Corros. Sci., 2012, 61: 123
5	Geng J, Tsakiropoulos P. A study of the microstructures and oxidation of Nb-Si-Cr-Al-Mo in situ composites alloyed with Ti, Hf and Sn [J]. Intermetallics, 2007, 15: 382
6	Zelenitsas K, Tsakiropoulos P. Effect of Al, Cr and Ta additions on the oxidation behaviour of Nb-Ti-Si in situ composites at 800 ^oC [J]. Mater. Sci. Eng., 2006, 416A: 269
7	Sun Z P, Guo X P, Tian X D, et al. Effects of B and Si on the fracture toughness of the Nb-Si alloys [J]. Intermetallics, 2014, 54: 143
8	Liu Z D, Hou S X, Liu D Y, et al. An experimental study on synthesizing submicron MoSi₂-based coatings using electrothermal explosion ultra-high speed spraying method [J]. Surf. Coat. Technol., 2008, 202: 2917
9	Qiao Y Q, Guo X P. Formation of Cr-modified silicide coatings on a Ti-Nb-Si based ultrahigh-temperature alloy by pack cementation process [J]. Appl. Surf. Sci., 2010, 256: 7462
10	Wei L, Shao W, Li M F, et al. Hot corrosion behaviour of Mo-62Si-5B (at.%) alloy in different molten salts at 900 ^oC [J]. Corros. Sci., 2019, 158: 108099
11	Pang J, Wang W, Zhou C G. Microstructure evolution and oxidation behavior of B modified MoSi₂ coating on Nb-Si based alloys [J]. Corros. Sci., 2016, 105: 1
12	Sakidja R, Park J S, Hamann J, et al. Synthesis of oxidation resistant silicide coatings on Mo-Si-B alloys [J]. Scr. Mater., 2005, 53: 723
13	Chen Z, Shao W, Li M F, et al. Effect of minor B modification on the oxidation behavior of MoSi₂ alloy at high temperature [J]. Corros. Sci., 2023, 216: 111070
14	Wen S H, Zhou C G, Sha J B. Microstructural evolution and oxidation behaviour of Mo-Si-B coatings on an Nb-16Si-22Ti-7Cr-2Al-2Hf alloy at 1250 ^oC prepared by spark plasma sintering [J]. Surf. Coat. Technol., 2018, 352: 320
15	Du W, Zhang L Q, Ye F, et al. Intrinsic embrittlement of MoSi₂ and alloying effect on ductility: studied by first-principles [J]. Phys. Condens. Matter, 2010, 405B: 1695
16	Wang S, Pang X J, Xu Y J, et al. Microstructure, mechanical and tribological properties of in situ MoB reinforced Cu-Al matrix composites [J]. Tribol. Int., 2023, 177: 107941
17	Segall M D, Lindan P J D, Probert M J, et al. First-principles simulation: ideas, illustrations and the CASTEP code [J]. J. Phys. Condens. Matter, 2002, 14: 2717
18	Ma K K, Schoenung J M. Isothermal oxidation behavior of cryomilled NiCrAlY bond coat: homogeneity and growth rate of TGO [J]. Surf. Coat. Technol., 2011, 205: 5178
19	Fischer T H, Almlöf J. General methods for geometry and wave function optimization [J]. J. Phys. Chem., 1992, 96: 9768
20	Ritt P, Sakidja R, Perepezko J H. Mo-Si-B based coating for oxidation protection of SiC-C composites [J]. Surf. Coat. Technol., 2012, 206: 4166
21	Lemberg J A, Ritchie R O. Mo-Si-B alloys for ultrahigh-temperature structural applications [J]. Adv. Mater., 2012, 24: 3445
22	Delley B. Analytic energy derivatives in the numerical local-density-functional approach [J]. J. Chem. Phys., 1991, 94: 7245
23	Zheng H Z, Chen Z, Li G F, et al. High-temperature corrosion mechanism of YSZ coatings subject to calcium-magnesium-aluminosilicate (CMAS) deposits: first-principles calculations [J]. Corros. Sci., 2017, 126: 286
24	Zoroddu A, Bernardini F, Ruggerone P, et al. First-principles prediction of structure, energetics, formation enthalpy, elastic constants, polarization, and piezoelectric constants of AlN, GaN, and InN: comparison of local and gradient-corrected density-functional theory [J]. Phys. Rev., 2001, 64B: 045208
25	Zhang J H, Duan Y H, Li C X. A First-principles investigation of structural properties, electronic structures and optical properties of β- and γ-LiAl(SiO₃)₂ [J]. Ceram. Int., 2017, 43: 13948
26	Yoshimi K, Nakatani S, Suda T, et al. Oxidation behavior of Mo₅SiB₂-based alloy at elevated temperatures [J]. Intermetallics, 2002, 10: 407

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