高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    

碳纳米管/碳酸钙共包覆超疏水镁钙砂及其抗水化性能

王鑫1,2，张令1，张海军1，王军凯2   

  1. 1. 武汉科技大学 先进耐火材料全国重点实验室 2. 河南理工大学 材料科学与工程学院
  • 收稿日期:2025-08-01 修回日期:2025-09-17 网络首发:2025-09-18 发布日期:2025-09-18
  • 通讯作者: 张海军 E-mail:zhanghaijun@wust.edu.cn
  • 基金资助:
    国家自然科学基金项目（批准号：U23A20559, 52272021, 52102017, 52232002）资助

Hydration resistance of CNTs/CaCO3 co-coated superhydrophobic MgO-CaO grains

WANG Xin1, 2, ZHANG Ling1, ZHANG Haijun1, *, WANG Junkai2   

  1. 1. State Key Laboratory of Advance Refractories, Wuhan University of Science and Technology 2. School of Materials Science and Engineering, Henan Polytechnic University, Jiaozuo
  • Received:2025-08-01 Revised:2025-09-17 Online First:2025-09-18 Published:2025-09-18
  • Contact: ZHANG Haijun E-mail:zhanghaijun@wust.edu.cn
  • Supported by:
    Supported by the National Natural Science Foundation of China (No. U23A20559, 52272021, 52102017, 52232002)

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摘要： MgO-CaO耐火材料因其高的耐火度、优异的抗渣侵蚀性、良好的热力学稳定性及净化钢水能力，被广泛应用于连铸中间包等炉衬，然而该材料极易潮解水化的特性严重限制了其应用。为提升镁钙材料的抗水化性能，本文以大豆油为碳源，以Co为催化剂，采用催化化学气相沉积法一步合成了碳纳米管（CNTs）与碳酸钙（CaCO3）共包覆的超疏水镁钙砂。系统研究了反应温度、催化剂用量及保温时间对制备改性镁钙砂结构与抗水化性能的影响。结果表明：制备CNTs-CaCO3共包覆超疏水镁钙砂的最佳条件为700℃、保温1 h、2 wt% Co催化剂。所得改性镁钙砂的水接触角高达155°，在70℃、85%相对湿度、24 h水化的条件下，水化增重仅为0.73 wt%，抗水化性能较未改性镁钙砂提升了9.47倍。疏水的CNT层与CaCO3保护壳的协同作用有效抑制了水的渗透与水化反应。研究结果为MgO-CaO材料抗水化性能的提高提供了一种简便的制备方法。

关键词: 镁钙砂, 抗水化, 碳纳米管/碳酸钙共包覆, Co催化剂

Abstract: Magnesia-calcia (MgO-CaO) refractories are widely used in tundish linings and continuous casting furnaces owing to their high melting point, thermal stability, resistance to slag corrosion, and effectiveness in purifying molten steel. However, their susceptibility to hydration in humid environments severely limits their practical applications. To enhance the hydration resistance of MgO-CaO materials, this study presents a novel one-step catalytic chemical vapor deposition method using soybean oil as a carbon source and cobalt (Co) as a catalyst to synthesize carbon nanotubes (CNTs) and calcium carbonate (CaCO3) co-coated superhydrophobic MgO-CaO grains. The effects of pyrolysis temperature, catalyst loading, and holding time on the microstructure and hydration resistance of the modified MgO-CaO grains were systematically investigated. The results indicate that the optimal synthesis conditions for the CNTs-CaCO3 co-coated superhydrophobic MgO-CaO grains are as follows: a reaction temperature of 700?°C, a holding time of 1?h, and 2?wt% Co catalyst loading. Under these conditions, the modified aggregates exhibited a water contact angle of 155°, and a minimal hydration-induced weight gain of only 0.73?wt% after exposure to 70?°C and 85% relative humidity for 24 h, representing a 9.47-fold improvement in hydration resistance compared to unmodified grains. The synergistic protective effects of the hydrophobic CNT layer and the CaCO3 shell effectively hindered moisture ingress and subsequent hydration reactions. This study provides an facile and efficient approach for enhancing the hydration resistance of MgO-CaO refractories.

Key words: MgO-CaO grains, Hydration resistance, CNT/CaCO3 co-coated, Co catalyst

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