功能化新型耐火材料的設計、制備及應用

王恩會; 陳俊紅; 侯新梅

doi:10.13374/j.issn2095-9389.2019.07.04.033

功能化新型耐火材料的設計、制備及應用

doi: 10.13374/j.issn2095-9389.2019.07.04.033

1.
北京科技大學鋼鐵共性技術協同創新中心，北京 100083
2.
北京科技大學材料科學與工程學院，北京 100083

基金項目: 國家自然科學基金資助項目(51904021，51974021，51874027)；中央高校基本科研業務費資助項目（FRF-TP-19-008A1）；國家優秀青年基金資助項目(51522402)

詳細信息

通訊作者:
E-mail：houxinmei01@126.com

中圖分類號: TG142.71
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- 被引次數: 0
出版歷程
- 收稿日期: 2019-07-04
- 刊出日期: 2019-12-01

Design, preparation, and application of new functional refractories

1.
Collaborative Innovation Center of Steel Technology, University of Science and Technology Beijing, Beijing 100083, China
2.
School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China

More Information

Corresponding author: E-mail: houxinmei01@126.com

摘要

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。
- 耐火材料 /
- 結構設計 /
- 可控制備 /
- 高品質鋼 /
- 工業應用
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.
- refractory /
- microstructure design /
- controllable preparation /
- high-quality steels /
- industrial application

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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

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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

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圖 3 1900 ℃條件下Al–Si–C–O體系氣相分壓圖^[22]

Figure 3. Equilibrium partial pressures of gases as a function of P_CO for 1900 ℃^[22]

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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 ℃

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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 ℃

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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 ℃

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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 ℃

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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)

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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

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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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