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摘要: 圍繞含Ti不銹鋼冶金工藝的研究進展，從冶金物理化學基礎、氧化物和TiN夾雜的形成與控制、凝固過程TiN復合核心和Ti元素對不銹鋼鑄件力學性能的影響等方面進行了總結和討論。主要的研究進展為：含Ti不銹鋼在冶煉過程生成的Al2O3、鎂鋁尖晶石、(MgO?Al2O3)rich?CaO?TiOx等高熔點氧化物夾雜是導致含鈦不銹鋼連鑄水口堵塞的主要原因；優化的Al、Ca、Ti的添加方式和爐渣控制工藝是夾雜物減少和低熔點化的重要手段；TiN夾雜的析出、擴散長大和碰撞聚合的基本規律是關注的熱點，鋼液中大尺寸氧化物夾雜會促進TiN團簇的形成；通過嚴格控制凝固過程TiN或氧化物-TiN復合核心能夠促進δ-Fe異質形核，提高連鑄坯等軸晶率；固溶Ti元素能提高奧氏體或雙相不銹鋼中鐵素體含量，提升不銹鋼鑄件的拉伸性能。Abstract: Titanium is widely used in the manufacture of stainless steel due to its stabilizing ability of carbon and nitrogen, the pinning effect on grain growth, and strengthening effect, which are contributed by the formation of Ti(C, N) with different compositions, sizes, and distributions. Due to the excellent corrosion resistance, formability, and mechanical properties, Ti-bearing stainless steel is widely applied to daily life and priority industries, including petroleum, aerospace, nuclear power, and transportation. However, complex inclusions can be formed after Ti addition in the metallurgy process. Moreover, those inclusions have adverse effects on the metallurgy and the quality of stainless steel, including the clogging of the submerged entry nozzle, layered defects, and surface defects. Therefore, it is important to develop the metallurgy of Ti-stabilized stainless steel. This paper discussed and concluded the investigation development of Ti-bearing stainless steel regarding the fundamentals of metallurgy, the formation and control of oxides and TiN, heterogeneous nucleation, and the influence of Ti on the mechanical properties of stainless steel. First, oxides with high melting points, including Al2O3, spinel, and (MgO?Al2O3)rich?CaO?TiOx, generally cause the clogging of the submerged entry nozzle in the Ti-bearing stainless steel. The optimized addition of Al, Ca, and Ti, as well as the control of slag, can decrease the amount of oxides with a high melting point. Second, the formation and growth of TiN and complex TiN inclusions happen during the cooling and the solidification of the titanium-stabilized stainless steel, which can collide and aggregate to form TiN clusters. Moreover, macro-oxides can promote the formation of TiN clusters. However, TiN or complex TiN inclusions can also work as heterogeneous nuclei for δ-Fe during the solidification of stainless steel and promote the generation of an equiaxed fine-grain structure. In addition to forming compounds, titanium can present as a solid solution state in steel and promote the formation of ferrite in austenitic stainless steel or increase the ferrite fraction in duplex stainless steel with its strong ferrite forming ability, which is beneficial to the improvement of the mechanical properties of stainless steel casting.
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Key words:
- stainless steel /
- inclusions /
- TiN /
- solidification structure /
- heterogeneous nuclei
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圖 1 不銹鋼中TiN穩定相圖。（a）18Cr鐵素體不銹鋼；（b）18Cr–8Ni奧氏體不銹鋼
Figure 1. Stability diagram of TiN in stainless steel: (a) 18Cr stainless steel; (b) 18Cr–8Ni stainless steel
圖 2 水口堵塞物形貌及成分
Figure 2. Morphology and composition of the deposits in the submerged entry nozzle
圖 3 1600 ℃時鐵素體不銹鋼中Al?Ti?O平衡相圖。（a）11Cr鐵素體不銹鋼；（b）20Cr鐵素體不銹鋼
Figure 3. Stability diagram of the Al–Ti–O system in stainless steel at 600 ℃: (a) Fe–11Cr stainless steel; (b) Fe–20Cr stainless steel
圖 4 1600 ℃時鐵素體不銹鋼中Al?Mg?O平衡相圖。（a）Fe?20Cr?Al?Mg?O；（b）加入5×10?6Ca 的Fe?20Cr?Al?Mg?O
Figure 4. Stability diagram of the Al–Mg–O system in stainless steel at 1600 ℃: (a) Fe–20Cr–Al–Mg–O; (b) Fe–20Cr–Al–Mg–O containing 5×10?6Ca
圖 5 不同冷卻速度及Ti，N質量分數下，K418合金凝固過程中TiN夾雜的長大行為
Figure 5. Growth of TiN during the solidification of K418 alloy with different cooling rates, contents of Ti and N
圖 6 TiN團簇（a）和MgO?TiN復合夾雜（b）
Figure 6. TiN clusters (a) and MgO–TiN complex inclusions (b)
圖 8 Ti合金化對鑄態組織的影響。（a）不含Ti的鑄錠；（b）含Ti鑄錠
Figure 8. As-cast structure of ferritic stainless steel: (a) without Ti addition; (b) with Ti addition
圖 9 快速冷卻后液滴組織形貌（a）和形核核心（b, c）
Figure 9. Microstructure of ferritic stainless steel droplet after rapid cooling (a) and heterogeneous nucleation of δ-Fe (b, c)
圖 10 不同Ti質量分數的Fe–20Cr–8Ni不銹鋼微觀組織。（a, b）0.0036% Ti；（c, d）0.2%Ti；（e, f）0.45% Ti
Figure 10. Microstructure of Fe–20Cr–8Ni stainless steel with different Ti contents: (a, b) 0.0036% Ti; (c, d) 0.2% Ti; (e, f) 0.45% Ti
表 1 350 ℃時不同Ti含量鑄錠的拉伸性能
Table 1. Tensile properties of ingots with different Ti contents at 350 ℃
Ingot Mass fraction
of Ti/ %Yield strength /
MPaUltimate tensile
strength / MPaTensile
elongation /%S1 0.0036 207.41 452.31 31.20 S2 0.20 229.11 471.27 30.92 S3 0.45 238.89 494.87 31.20 
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