第一性原理分子动力学研究<strong>MnO</strong>对埋弧焊剂导电机制的影响

doi:10.11900/0412.1961.2025.00065

金属学报

2026, Vol. 62

Issue (1): 191-202 DOI: 10.11900/0412.1961.2025.00065

研究论文

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第一性原理分子动力学研究MnO对埋弧焊剂导电机制的影响

袁航¹^,², 张燕云¹^,², 王聪¹^,²(

)

1 东北大学冶金学院沈阳 110819
2 东北大学辽宁省厚板焊接冶金工程研究中心沈阳 110819

Influence of MnO upon Electrical Conductive Mechanisms of Submerged Arc Welding Fluxes: Insights from Ab Initio Molecular Dynamics Simulations

YUAN Hang¹^,², ZHANG Yanyun¹^,², WANG Cong¹^,²(

)

1 School of Metallurgy, Northeastern University, Shenyang 110819, China
2 Liaoning Engineering Research Centre for Thick Plate Welding Metallurgy, Northeastern University, Shenyang 110819, China

引用本文:

袁航, 张燕云, 王聪. 第一性原理分子动力学研究MnO对埋弧焊剂导电机制的影响[J]. 金属学报, 2026, 62(1): 191-202.
Hang YUAN, Yanyun ZHANG, Cong WANG. Influence of MnO upon Electrical Conductive Mechanisms of Submerged Arc Welding Fluxes: Insights from Ab Initio Molecular Dynamics Simulations[J]. Acta Metall Sin, 2026, 62(1): 191-202.

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摘要:

为了研究焊剂中离子导电和电子导电的具体机制，本工作采用四电极法测量了CaF₂-SiO₂-Al₂O₃-MgO(MnO)焊剂的电导率，并结合第一性原理分子动力学模拟，探究了离子导电和电子导电对总电导率的贡献机制。结果表明，在无MnO体系中，Mg²⁺、Ca²⁺和F^-为主要载流子进行离子导电，其扩散行为受网络结构聚合度的限制。引入MnO后，硅铝酸盐网络结构聚合度先升后降，促使离子导电能力呈现先降后升的波动趋势；电子导电能力则持续增强，其原因在于MnO降低了O和F周围的电子局域化程度，提升了Mn原子的电荷转移能力并拓宽了电子跃迁通道。在离子和电子复合导电机制下，MnO对电子导电的促进作用远强于对离子导电的影响。合理调控MnO含量是有效提升焊剂导电性能的重要策略。

关键词 ：焊剂, 电导率, 第一性原理分子动力学, 结构聚合度, 电子结构

Abstract：

Submerged arc welding (SAW) is a widely used technique for joining oil and gas pipelines and shipbuilding steels. During SAW, fluxes are critical for atmospheric shielding, weld metal refinement, and heat loss prevention. Their electrical conductivity—a key temperature- and composition-dependent property—dictates arc stability and weld pool heat distribution. However, the mechanisms governing ionic and electronic conduction remain inadequately understood. This study explores the conductivity of CaF₂-SiO₂-Al₂O₃-MgO(MnO) fluxes using a combination of four-electrode experimental measurements and ab initio molecular dynamics simulations, systematically analyzing contributions from ionic and electronic conduction. The results demonstrate that substituting MgO with MnO induces fluctuations in ionic conductivity, primarily owing to competing effects of structural polymerization and ion diffusion. Specifically, the degree of polymerization in Si and Al polyhedral structures and the proportion of bridging oxygens initially increase but later decrease with MnO addition. A general trend is observed in ionic diffusion coefficients, reflecting a balance between structural rigidity and ion mobility. However, MnO consistently enhances electronical conductivity. As MnO content increases, the partial density of states of Mn near the Fermi level rises considerably, indicating improved electron mobility. MnO facilitates electron migration by reducing electron localization around O and F atoms. Furthermore, the increased Bader charge on Mn atoms suggests enhanced charge transfer between Mn and O, thereby creating additional pathways for electron hopping. Consequently, the overall conductivity increases markedly with elevated MnO content, enabled by a consistent rise in electronical conductivity that outweighs fluctuating ionic contributions. These findings underscore the dominant role of electronic conduction in enhancing slag conductivity and the need for future efforts toward optimizing electronic transport through the rational design of transition metal oxides.

Key words： welding flux electrical conductivity ab initio molecular dynamics simulation structural polymerization electronic structure

收稿日期: 2025-03-12

ZTFLH:

TG445

基金资助:国家重点研发计划项目(2023YFB3709900);国家自然科学基金项目(W2411047);国家自然科学基金项目(52404393);中央高校基本科研业务费项目(N2402016)

通讯作者: 王聪，wangc@smm.neu.edu.cn，主要从事焊接冶金研究

作者简介: 袁航，男，1995年生，博士生

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https://www.ams.org.cn/CN/10.11900/0412.1961.2025.00065 或 https://www.ams.org.cn/CN/Y2026/V62/I1/191

表1 焊剂熔融前后的化学成分及开始熔化温度 (mass fraction / %)

图1 目标体系XRD谱及电导率

图2 目标体系中原子对的径向分布函数曲线及F3样品中原子对的配位数

图3 目标体系中不同类型O和F以及Si多面体(QSi)和Al多面体(QAl)单元的占比

图4 目标体系中离子的均方根位移(MSD)和数据拟合结果及扩散系数

图5 第一性原理分子动力学(AIMD)模拟目标体系中最后10 ps的原子轨迹(2000 K)

图6 目标体系中不同元素的分波态密度和总态密度

图7 不同原子构型下的电子局域化函数(ELF)分布图及Mn—O/F和Mg—O/F的ELF分布

图8 目标体系中的Bader电荷

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