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摘要: 大尺寸CaO?Al2O3類夾雜物容易引起軸承鋼疲勞失效，大尺寸CaO?Al2O3類夾雜物的控制是生產高端GCr15軸承鋼的關鍵因素之一。精煉過程中合金引入雜質元素、渣精煉和精煉過程中卷渣是鋁脫氧軸承鋼中大尺寸CaO?Al2O3類夾雜物的主要潛在來源。硅鐵合金通常用來提高軸承鋼的淬火和抗回火軟化性。本文通過實驗室實驗、樣品分析和熱力學計算，研究了硅鐵合金中金屬鈣元素對鋁脫氧鋼中夾雜物的影響。硅鐵合金主要由深色的硅相和淺色的硅鐵相組成，鈣元素在硅相和硅鐵相的界面處以金屬化合物形式存在。研究發現，加入硅鐵合金后，鋼中總鈣（T.Ca）含量增加，鋼中的Al2O3和MgO·Al2O3夾雜物被改性為CaO?Al2O3類夾雜物，夾雜物尺寸隨著夾雜物中CaO含量增加而減小，鋼中并未生成大尺寸CaO?Al2O3類夾雜物。隨著鋼中T.Ca含量增加，夾雜物平均尺寸降低，鋼中T.O含量增加，表明硅鐵合金中金屬鈣元素不會直接引起鋼中大尺寸CaO?Al2O3類夾雜物的生成。但是生成的小尺寸固相CaO?Al2O3類夾雜物在水口處粘附結瘤，結瘤物脫落后會成為鋼中大尺寸CaO?Al2O3類夾雜物的來源之一。
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關鍵詞:
- 鋁脫氧鋼 /
- 硅鐵合金 /
- 金屬鈣元素 /
- CaOAl2O3類夾雜物 /
- 潔凈度
Abstract: Large CaO?Al2O3-type inclusions easily induce fatigue failure of bearing steels, so controlling large CaO?Al2O3-type inclusions is the key to producing high-quality GCr15-bearing steel. Impurity elements in alloys added during refining, slag refining, and slag entrainment during the refining process are the main potential sources for forming large CaO?Al2O3-type inclusions in Al-killed bearing steels. The ferrosilicon alloy is applied to improve the quenching and tempering softening resistance of Al-killed bearing steels. In this work, the effect of the calcium element in ferrosilicon alloys on inclusions in Al-killed bearing steel was studied through laboratory experiments, observations, and thermodynamic calculations. The ferrosilicon alloy mainly consists of the dark silicon and light ferrosilicon phases. The calcium element in ferrosilicon alloys exists as a metal compound at the interface between the silicon phase and the ferrosilicon phase. The total calcium (T.Ca) content in molten steel increases after adding the ferrosilicon alloy and modifying the Al2O3 and MgO·Al2O3 inclusions into CaO?Al2O3-type ones. The size of inclusions in the molten steel decreases with an increase in the CaO content in the inclusions. Large CaO?Al2O3-type inclusions are rarely generated. With the increase of the T.Ca in the molten steel, the T.O in the steel increases, whereas the average size of the inclusions decreases. It was observed that the calcium element in ferrosilicon alloys is not the direct cause for the formation of large size CaO?Al2O3 inclusions in the steel. However, the generated small, solid CaO?Al2O3-type inclusions clog the wall of the submerged entry nozzle, leading to dislodging of the big clogging lump into the molten steel. This lump is one of the reasons for large and irregularly shaped CaO?Al2O3 type inclusions in the steel product.-
Key words:
- Al-killed steel /
- ferrosilicon alloys /
- calcium element /
- CaO?Al2O3 type inclusions /
- cleanliness
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圖 1 不同鈣質量分數的硅鐵合金樣品的元素面掃描. (a) 0.68%; (b) 0.92%; (c) 1.22%
Figure 1. Elemental mapping of ferrosilicon alloys containing various T.Ca mass fraction: (a) 0.68%; (b) 0.92%; (c) 1.22%
圖 2 實驗室實驗后得到的鋼錠樣品分析示意圖
Figure 2. Schematic diagram analysis of the ingot sample after experiments
圖 3 加不同鈣含量的硅鐵條件下鋼中夾雜物成分分布. (a) 未加硅鐵; (b) 0.68% T.Ca; (c) 0.92% T.Ca; (d) 1.22% T.Ca
Figure 3. Composition distribution of inclusions in the steel on adding various types of ferrosilicon alloys: (a) not adding a ferrosilicon alloy; (b) 0.68% T.Ca; (c) 0.92% T.Ca; (d) 1.22% T.Ca
圖 4 不加硅鐵條件下鋼中典型夾雜物形貌. (a) Al2O3; (b) MgO·Al2O3; (c) Al2O3?(MgO?CaO)
Figure 4. Morphologies of typical inclusions in the steel without adding a ferrosilicon alloy: (a) Al2O3; (b) MgO·Al2O3; (c) Al2O3?(MgO?CaO)
圖 5 加入鈣質量分數1.22%的硅鐵條件下鋼中典型夾雜物形貌. (a) CaO?Al2O3?(MgO); (b) CaO?Al2O3?(MgO); (c) MgO?Al2O3?(CaO)
Figure 5. Morphologies of typical inclusions in the steel after adding the ferrosilicon alloy containing 1.22% T.Ca: (a) CaO?Al2O3?(MgO); (b) CaO?Al2O3?(MgO); (c) MgO?Al2O3?(CaO)
圖 6 鋼中鈣質量分數和夾雜物成分隨著加入含鈣不同的硅鐵合金的變化
Figure 6. Variation in the calcium content and the composition of steel inclusions after adding ferrosilicon alloy containing different calcium contents
圖 7 硅鐵合金的加入對鋼中夾雜物數量的影響. (a) 不同尺寸; (b) 不同成分
Figure 7. Effect of adding ferrosilicon alloy on the number of inclusions in the steel: (a) various sizes; (b) various compositions
圖 8 浸入式水口結瘤物三維形貌. (a) MgO?Al2O3?(CaO); (b) MgO?Al2O3?CaO; (c) CaO?Al2O3?(MgO)
Figure 8. Three-dimensional morphologies of clogging materials on the submerged entry nozzle: (a) MgO?Al2O3?(CaO); (b) MgO?Al2O3?CaO; (c) CaO?Al2O3?(MgO)
圖 9 浸入式水口不同位置處結瘤物成分
Figure 9. Composition of clogging materials at various locations of the submerged entry nozzle
圖 10 加入不同含鈣量的硅鐵條件下鋼中夾雜物和水口結瘤物的成分對比. (a) 未加硅鐵; (b) 0.68% T.Ca; (c) 0.92% T.Ca; (d) 1.22% T.Ca
Figure 10. Composition comparison of clogging materials on the submerged entry nozzle and inclusions in the steel by adding ferrosilicon alloy containing different T.Ca contents: (a) not adding ferrosilicon alloy; (b) 0.68% T.Ca; (c) 0.92% T.Ca; (d) 1.22% T.Ca
圖 11 不加硅鐵條件下鋼中夾雜物成分和尺寸的關系. (a) CaO質量分數和Al2O3質量分數; (b) MgO質量分數
Figure 11. Relationship between the size and composition of steel inclusions without adding ferrosilicon alloy: (a) CaO content and Al2O3 content; (b) MgO content
圖 12 加入含鈣0.68%的硅鐵條件下鋼中夾雜物成分和尺寸的關系. (a) CaO質量分數和Al2O3質量分數; (b) MgO質量分數
Figure 12. Relationship between the size and composition of steel inclusions after adding ferrosilicon alloy containing 0.68% T.Ca: (a) CaO content and Al2O3 content; (b) MgO content
圖 13 加入鈣質量分數0.92%的硅鐵條件下鋼中夾雜物成分和尺寸的關系. (a) CaO質量分數和Al2O3質量分數; (b) MgO質量分數
Figure 13. Relationship between the size and composition of steel inclusions after adding ferrosilicon alloy containing 0.9% T.Ca: (a) CaO content and Al2O3 content; (b) MgO content
圖 14 加入鈣質量分數1.22%的硅鐵條件下鋼中夾雜物成分和尺寸的關系. (a) CaO質量分數和Al2O3質量分數; (b) MgO質量分數
Figure 14. Relationship between the size and composition of steel inclusions after adding ferrosilicon alloy containing 1.22% T.Ca: (a) CaO content and Al2O3 content; (b) MgO content
圖 15 實驗室加硅鐵實驗鋁脫氧鋼中夾雜物尺寸隨著夾雜物中CaO含量的變化
Figure 15. Relationship between the CaO content and the diameter of inclusions in the Al-killed steel after adding ferrosilicon alloy containing different T.Ca contents
圖 16 鋼中T.Ca含量對夾雜物平均尺寸和T.O含量的影響. (a) 夾雜物平均尺寸; (b) T.O含量
Figure 16. Effect of the T.Ca content on the average diameter of inclusions and the T.O content in the steel: (a) average diameter of inclusions; (b) T.O content
圖 17 1873 K下向鋼中加入硅鐵合金引起的鈣含量增加對鋁脫氧鋼中夾雜物的影響. (a) T.O為 15×10?6; (b) T.O為8×10?6
Figure 17. Effect of the T.Ca content in the steel from ferrosilicon addition on the number of inclusions in the Al-killed steel at 1873 K: (a) T.O of 15×10?6; (b) T.O of 8×10?6
圖 18 1873 K下硅鐵合金加入引起的鈣含量增加對鋁脫氧鋼中夾雜物成分的影響
Figure 18. Effect of the T.Ca content in the steel from ferrosilicon addition on the inclusion composition in the Al-killed steel at 1873 K
表 1 硅鐵合金中鈣和鋁的質量分數
Table 1. Mass fraction of T.Ca and T.Al in ferrosilicon alloys
% Ferrosilicon T.Ca T.Al Type A 0.68 1.11 Type B 0.92 1.28 Type C 1.22 1.84 
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表 2 實驗后鋼成分（質量分數）
Table 2. Steel compositions after experiments
% Ferrosilicon C Cr Si Mn T.S T.Al T.Ca T.O Fe No addition 0.99 1.57 0.31 0.38 0.001 0.030 0.0001 0.0010 Balanced Type A 0.97 1.57 0.63 0.38 0.001 0.033 0.0003 0.0011 Balanced Type B 0.96 1.57 0.62 0.38 0.001 0.036 0.0004 0.0013 Balanced Type C 1.00 1.57 0.65 0.38 0.001 0.037 0.0010 0.0015 Balanced
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中文字幕在线观看表 3 文獻報道的 1873 K下γIG，θ，α和計算的對應c，Wad
Table 3. Reported γIG, θ, α from literatures, and calculated c, Wad
Mass fraction of inclusions/% $\gamma_{\text{IG} }$/(J·m?2) $ \theta $/(°) $ \alpha $/(°) $\gamma_{\text{MI} }$/(J·m?2) $ c $ $W_{\text{ad} }$/(J·m?2) CaO Al2O3 MgO 58.0 42.0 0 0.688[37] 54.3[37] 35.7[37] 1.206 0.577 1.178 49.4 50.6 0 0.669[37] 58.1[37] 38.6[37] 1.245 0.581 1.120 36.4 63.4 0 0.684[37] 65.9[37] 44.8[37] 1.303 0.587 1.077 20.0 80.0 0 0.619[41] 112.7[42] — 1.273 0.584 1.041 15.0 85.0 0 0.638[41] 112.7[42] — 1.292 0.586 1.041 10.0 90.0 0 0.659[41] 115.2[42] — 1.381 0.596 0.974 5.0 95.0 0 0.692[41] 123.4[42] — 1.626 0.620 0.762 0 71.7 28.3 0.512[43] 140.2[44] — 1.815 0.637 0.393 0 100.0 0 0.750[36] 144.0[45] — 2.122 0.661 0.324
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