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鋼液鈣處理過程有效鈣硫比對303 t超大鋼錠中硫化物形貌的影響

Effect of effective Ca/S ratio on sulfide morphology in a 303-ton heavy steel ingot with calcium treatment in molten steel

  • 摘要: 通過工業實驗研究了鈣處理對303 t的16Mn重型管板鑄錠中硫化物形貌的控制. 未鈣處理的鍛件缺陷主要分布在軸向上靠近頂部、徑向上在距中心1/2以內位置,缺陷主要為大尺寸Ⅱ類MnS夾雜物. 采用Micro-CT檢測了鑄錠頂部中心位置MnS夾雜物三維分布,夾雜物為長條狀和片狀,數密度為0.77 mm?3,最大直徑為1370 μm. 在真空脫氣后對鋼液進行鈣處理,鈣處理不僅將鋼液中原生Al2O3夾雜物改性為液態鈣鋁酸鹽,并且鈣會在鋼液凝固和冷卻過程中優于錳先與硫結合生成CaS. 通過FactSage熱力學計算得到,鈣處理將MnS夾雜物的析出溫度由1244.7 ℃降低至1227.9 ℃,同時減少了MnS夾雜物析出量. 鈣在改性硫化物之前先改性了鋼中氧化物,因此提出了有效鈣硫比Ca/Seff.用來表征鈣處理對硫化物形貌的影響,Ca/Seff.的含義為改性硫化物的有效鈣和鋼中硫的原子濃度比,可以直接根據鋼液的總氧T.O含量、總硫T.S含量和總鈣T.Ca含量計算得到,此公式適用于硫質量分數小于30×10?6的低硫鋼. 隨著鋼中Ca/Seff.增加,鑄錠頂部硫化物長寬比逐漸減小. 鈣處理后鋼中有效鈣硫比Ca/Seff.應大于0.8,鑄錠頂部硫化物平均長寬比小于1.2,CaS和MnS復合硫化物以鈣鋁酸鹽夾雜物為核心析出,硫化物為球形且尺寸顯著減小,此時鈣處理改性鑄錠中硫化物效果較好.

     

    Abstract: This paper investigated the effect of calcium treatment on the sulfide morphology of 303-ton 16Mn tube sheet ingots through industrial experiments. The defects in forgings without calcium treatment were mainly distributed axially near the top of the ingot and radially within half of the ingot center. The defects were mainly caused by large-size type II MnS inclusions. The three-dimensional distribution of MnS inclusions in the radial center of the ingot top was detected using a Micro-CT, and the MnS inclusions were mainly long strips and flake-shaped. The number density, average sphericity, and maximum diameter of the MnS inclusions were 0.77 mm?3, 0.53, and 1370 μm, respectively. In the industrial experiments, calcium treatment of molten steel was performed after vacuum-breaking during VD (Vacuum degassing) refining. Thermodynamic calculations were performed using FactSage 7.1 software. Calcium treatment modified the original solid Al2O3 inclusions into liquid calcium aluminate inclusions and reduced the precipitation temperature of MnS inclusions from 1244.7 ℃ to 1227.9 ℃. During the solidification and cooling process of the ingot, Ca preferentially combined with S to form CaS, which reduced the precipitation of MnS inclusions. Calcium modified the oxide inclusions in steel before modifying sulfides. Therefore, the effective calcium/sulfur ratio (Ca/Seff.) was proposed to characterize the effect of calcium treatment on the morphology of sulfides. Ca/Seff. is the atomic concentration ratio of effective calcium for modified sulfide to sulfur in steel. Ca/Seff. can be calculated by the total oxygen, sulfur, and calcium contents in steel. This formula is suitable for low sulfur steel with high cleanliness, and the mass fraction of sulfur in molten steel is >30×10?6. We analyzed the morphology of sulfide on the top of a Ca-treated heavy ingot. The effect of Ca/Seff. ratio on the morphology of the sulfide was studied by sampling every 1/4 from the radial center to the edge of the ingot. The aspect ratio of sulfide at the top of the ingot decreased gradually with increasing Ca/Seff. in steel. When Ca/Seff. in steel was 0.22, homogeneous MnS inclusions were observed in the sulfide, and the average aspect ratio was 1.59. After calcium treatment, the Ca/Seff. in the steel was greater than 0.8, and the average aspect ratio of sulfide at the top of the ingot was less than 1.2. CaS and MnS sulfide was precipitated with calcium aluminate inclusions as the core, and the precipitated sulfide was spherical with a significantly reduced size. Hence, calcium treatment effectively modified the sulfide in the ingot.

     

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