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凝固过程304不锈钢中钙改性夹杂物的转变行为

Transformation behavior of calcium-modified inclusions in 304 stainless steel during solidification

  • 摘要: 304不锈钢经钙改性后,钢中夹杂物的行为较为明晰,但对凝固过程中的演变规律仍缺乏系统认识。以钙改性304不锈钢为研究对象,结合实验室试验与热力学计算,系统研究了凝固过程中钙改性夹杂物的演变行为。结果表明,钢液中钙含量显著影响凝固过程中硫化物的析出类型与形态。低钙炉次中仅析出MnS,其析出方式包括以Al2O3-SiO2-CaO-MgO类夹杂物为异质形核核心及单独析出;高钙炉次中主要在原有夹杂物表面弥散析出大量CaS。炉冷后,高钙炉次夹杂物中Al2O3含量显著升高,SiO2含量降低,并伴有大量CaS析出;而低钙炉次中SiO2含量升高,Al2O3含量降低,且以MnS析出为主。炉冷后,钢中夹杂物尺寸增大,数量密度降低。热力学计算进一步揭示,随着钢中总钙(T.Ca)含量增加,夹杂物析出顺序为MnS+Ca2Al2SiO7→MnS+Ca2Al2SiO7+Ca2SiO4→MnS+Ca2Al2SiO7+Ca2SiO4+CaS → Ca2SiO4+MnS+CaS。在T.Ca一定时,随着总氧含量(T.O)增加,析出转变顺序为MnS+Ca2Al2SiO7+Ca2SiO4+CaS→MnS+Ca2Al2SiO7+Ca2SiO4→MnS+Ca2Al2SiO7+CaAl4O7+CaAl2Si2O8+Al2O3。

     

    Abstract: The behavior of inclusions in 304 stainless steel after calcium modification has been relatively well clarified, yet their evolution during solidification remains insufficiently understood. A systematic investigation was conducted on calcium-modified 304 stainless steel through laboratory experiments and thermodynamic calculations, focusing on the evolution of inclusions throughout solidification. The results indicate that the calcium content in molten steel significantly affects the type and morphology of sulfide precipitation. In low-calcium heats, only MnS precipitates, nucleating either heterogeneously on Al2O3-SiO2-CaO-MgO inclusions or independently from the melt. In high-calcium heats, abundant CaS particles precipitate dispersedly on the surfaces of pre-existing inclusions. After furnace cooling, the Al2O3 fraction in inclusions of high-calcium heats increases significantly, accompanied by a decrease in SiO2 and substantial CaS precipitation. Conversely, in low-calcium heats, theSiO2 fraction increases, the Al2O3 fraction decreases, and MnS predominates. Post-cooling, the inclusion size increases while the number density decreases. Thermodynamic calculations further reveal that with increasing total calcium (T.Ca) content, the precipitation sequence follows: MnS+Ca2Al2SiO7→MnS+Ca2Al2SiO7+Ca2SiO4→MnS+Ca2Al2SiO7+Ca2SiO4+CaS→Ca2SiO4+MnS+CaS. At a fixed T.Ca, an increase in total oxygen (T.O) shifts the sequence to MnS+Ca2Al2SiO7+Ca2SiO4+CaS→MnS+Ca2Al2SiO7+Ca2SiO4→MnS+Ca2Al2SiO7+CaAl4O7+CaAl2Si2O8+Al2O3.

     

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