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摘要: 圍繞兩種新型耐火材料展開，即鋼包精煉用高性能低碳鎂碳耐火材料以及超低氧鋼用耐火材料，初步實驗表明，將大尺寸的碳硅化鋁（Al4SiC4）引入到鎂碳磚（MgO?C）中不僅可以提高其抗氧化能力，又能對含碳耐火材料氧化后的疏松結構進行修復，有望成為新一代鋼包精煉用高性能低碳鎂碳耐火材料；CaO?MgO?Al2O3（CMA）材料兼具優異的熱機械和耐渣侵性能的同時，還可以在服役過程產生低熔點精煉渣相，具備凈化鋼水的潛力。可以預見，上述功能化新型耐火材料有望為高品質鋼的進一步發展提供有力材料支撐。Abstract: Every significant technical advancement of the steel industry has depended on the support of refractories used as lining materials in various smelting containers. With the increasing demand for high-quality steels, the precise control of inclusions has become increasingly important. Existing technologies and equipment can effectively reduce the amount and average size of inclusions, but they cannot guarantee the complete removal of large-sized ones. In the steel-making process, refractories in close contact with molten steel are a main source of large-sized non-metallic inclusions; these can become bottlenecks, restricting improvements in steel quality. Based on this problem, the design, preparation, and application of new functional refractories become a critical focus for further development in the steel industry. These refractories are required to possess not only excellent thermo-mechanical properties (i.e., zero or reduced contaminant for the molten steel), but also the ability to remove inclusions with a high melting point in molten steel. However, available refractories are in their primary stages depending on experience, resulting in no breakthroughs in the precise control of inclusions, and even contamination of molten steel. This study focused on two new refractory materials, namely large-sized Al4SiC4 with controllable morphology, and Al2O3?MgO?CaO (CMA) with a ternary-layer structure. Preliminary experiments show that, with the introduction of the large-sized Al4SiC4, oxidation resistance of MgO?C bricks is improved, and the loose structure resulting from the oxidation of carbon-containing materials can be repaired. CMA materials not only possess excellent thermo-mechanical properties and high slag resistance, but also can produce refining slag phases with a low melting point. This can contribute to the floating of inclusions, thus exhibiting the potential for purifying molten steel. These new, functional refractories should offer strong support for the further development of high-quality steels.
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圖 1 晶體結構示意圖. (a) Al4SiC4；(b)SiC單元晶體；(c) Al4C3單元 晶體
Figure 1. Schematic diagram of the crystal structure: (a) Al4SiC4; (b) SiC unit; (c) Al4C3 unit
圖 2 典型的Al4SiC4陶瓷形貌. (a)氧化表面；(b)橫截面
Figure 2. Typical morphologies of Al4SiC4 ceramic: (a) oxidized surface; (b) oxidized cross-section
圖 4 1900 ℃條件下碳熱還原制備Al4SiC4材料的物相分析結果
Figure 4. XRD pattern of Al4SiC4 synthesized via carbothermic method at 1900 ℃
圖 5 碳熱還原法在1900 ℃合成Al4SiC4晶體的掃描電鏡照片
Figure 5. SEM images of Al4SiC4 synthesized via carbothermic method at 1900 ℃
圖 6 不同溫度下Al4SiC4晶體的結構演變. (a) 1400 ℃；(b) 1500 ℃；(c) 1600 ℃
Figure 6. Evolution of Al4SiC4 crystal at different temperatures: (a) 1400 ℃；(b) 1500 ℃；(c) 1600 ℃
圖 7 體系中生成中的MgAl2O4的形貌. (a) 1400 ℃；(b) 1500 ℃；(c) 1600 ℃
Figure 7. Morphologies of MgAl2O4 in MgO–C system with Al4SiC4 added at different temperatures: (a) 1400 ℃; (b) 1500 ℃; (c) 1600 ℃
圖 8 1650 ℃條件下CaO–MgO–Al2O3三元相圖（部分）
Figure 8. Ternary phase diagram of CaO–MgO–Al2O3 at 1650 ℃ (partial)
圖 9 晶體結構示意圖. (a) CA6；(b) MA；(c) CM2A8；(d) C2M2A14
Figure 9. Schematic diagram of crystal structure: (a) CA6; (b) MA; (c) CM2A8; (d) C2M2A14
圖 10 1700 ℃熱壓后CM2A8的X射線衍射圖譜(a)、形貌表征(b)和結晶狀態表征(c)
Figure 10. CM2A8 ceramic after hot-press sintering at 1700 ℃: (a) XRD pattern; (b) morphological characterization; (c) crystalline state characterization
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圖 11 CM2A8的抗渣侵蝕實驗表征. (a)抗LF渣侵蝕；(b)抗RH渣侵蝕
Figure 11. Resistance behavior of CM2A8: (a) LF slag; (b) RH slag
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