电渣重熔易氧化元素控制的研究进展

Research progress on the control of reactive elements in remelted ingots during the electroslag remelting process

  • 摘要: 电渣重熔是重要的二次精炼技术,不仅可以去除钢中杂质元素和非金属夹杂物,还可以改善铸锭的凝固组织进而提升钢的力学性能. 若钢中含有易氧化合金元素,如Al、Ti、Si、B和稀土元素,会与CaF2‒CaO‒Al2O3基重熔渣系中的不稳定组元发生化学反应,造成合金元素沿铸锭高度方向分布不均匀现象. 为抑制电渣重熔过程易氧化元素的烧损,在电渣重熔温度范围内,分析CaF2‒CaO‒Al2O3基重熔渣系中各个组元对钢中目标控制元素含量的影响,可以实现重熔渣系成分的准确设计,这取决于渣相和合金相中组元活度的准确计算. 除了在重熔渣系中添加对应元素的氧化物之外,CaF2‒CaO‒Al2O3基重熔渣系中公共组元CaO和Al2O3以及温度对钢中不同合金元素含量的影响也并不相同. 电渣重熔过程传质模型预报结果的准确性依赖于对熔渣和钢液中组元的热力学活度、不同反应位置(电极端部、金属熔滴、渣池和金属熔池界面)温度、传质系数和几何参数的准确估计,但不同电渣重熔操作、重熔渣系成分和钢种对以上参数都有较大影响. 由于准确估计不同反应位置处的反应温度和流体流动对传质系数的影响比较困难,相比较热力学分析,易氧化元素反应的动力学研究仍比较匮乏. 重熔渣系物性参数对铸锭的表面和凝固质量同样有重要影响,目前对含TiO2、SiO2、B2O3和稀土氧化物的重熔渣系的物性参数研究主要集中在黏度和结晶能力等方面,但对其活度的实验室研究还未见报道. 低氟重熔渣系的开发越来越受到关注,针对低氟重熔渣系条件下钢中易氧化元素控制的热力学、动力学和熔渣物性参数研究还有待于进一步开展.

     

    Abstract: Electroslag remelting (ESR) is an important secondary refining technique that effectively removes impurities and nonmetallic inclusions, improves the solidification structure of ingots, and enhances the mechanical properties of steels. However, when steels contain easily oxidizable alloying elements such as Al, Ti, Si, B, and rare earth elements (REEs), strong chemical reactions can occur between these elements and unstable components in the CaF2–CaO–Al2O3-based ESR type slag system. These reactions take place in the slag–metal interface and result in uneven distribution of the alloying elements along the height of the remelted ingots, ultimately compromising the mechanical properties of the steels. To reduce the oxidation loss of these alloying elements during the ESR process, a precise design of the CaF2–CaO–Al2O3-based ESR slag composition is crucial. This design facilitates accurate control of the reactive alloying elements within their target composition range, which relies on the feasibility of calculating the thermodynamic activities of components in the slag and alloys employing ion–molecular coexistence theory and Wagner equation, respectively. In addition to incorporating the corresponding oxide additives into the ESR-type slag system to prevent oxidation loss of alloying elements in the electrode during the ESR process, the effects of common components such as CaO and Al2O3 in the ESR-type slag, as well as temperature, on the alloying element content can vary. For instance, controlling the Al and Ti contents in alloys is influenced by the combined effects of the CaO composition range and the remelting temperature, in addition to the presence of Al2O3 in the ESR-type slag. For B-bearing steels, the B content in alloys can be primarily controlled by the CaO content rather than by Al2O3. In the case of alloys containing REEs, such as La, Ce, and Y, the addition of CaO enhances the yield of these elements, while the addition of Al2O3 has a negative effect. The accuracy of mass transfer models during ESR not only relies on precise estimation of the thermodynamic activities of components in the slag and molten steel but also on factors such as temperatures at different reaction locations (e.g., electrode tip, metal droplet, interface between slag bath, and metal pool), mass transfer coefficients, and geometric parameters. However, the parameters above are substantially influenced by various factors, such as different ESR operation conditions, slag compositions, and steel grades. Due to the challenges in determining reaction temperatures and fluid flow within the ESR furnace, precisely estimating the mass transfer coefficients of the relative elements in the slag and metal phases at different reaction locations is difficult. Thus, kinetic studies of reactive elements are relatively scarce compared to thermodynamic analyses. Additionally, the physical parameters of the slag system play a crucial role in determining the surface quality and solidification characteristics of the ingots. Current research on the physical parameters of remelting slag systems containing TiO2, SiO2, B2O3, and rare earth oxides has primarily focused on viscosity and crystallization behavior. However, laboratory studies on the activities of these components remain limited. As the development of low-fluorine ESR-type slag systems attracts increasing attention, the need for relative fundamental research, specifically on the thermodynamics and physicochemical properties of low-fluorine slags, also rises. This research is essential for effectively controlling the contents of reactive alloying elements in the ESR remelted ingots.

     

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