CN107285786A - 钛铝酸钙‑碳化硅‑碳复相耐火材料及其制备方法 - Google Patents

钛铝酸钙‑碳化硅‑碳复相耐火材料及其制备方法 Download PDF

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CN107285786A
CN107285786A CN201710607566.4A CN201710607566A CN107285786A CN 107285786 A CN107285786 A CN 107285786A CN 201710607566 A CN201710607566 A CN 201710607566A CN 107285786 A CN107285786 A CN 107285786A
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calcium aluminate
titanium calcium
refractory material
silicon carbide
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CN107285786B (zh
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赵惠忠
陈建威
张寒
王相辉
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Wuhan University of Science and Engineering WUSE
Wuhan University of Science and Technology WHUST
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Abstract

本发明涉及一种钛铝酸钙‑碳化硅‑碳复相耐火材料及其制备方法。其技术方案是：以50~60wt%的钛铝酸钙颗粒、5~10wt%的碳化硅颗粒、10~20wt%的碳化硅细粉、5~10wt%的氧化铝微粉、10~20wt%的电熔棕刚玉细粉和2~4wt%的球状沥青为原料，外加所述原料3~4wt%的硅溶胶、0.05~0.2wt%的分散剂和4~6wt%的水，搅拌5~8min，振动成型，室温养护20~28h，于90~115℃条件下干燥20~24h，制得钛铝酸钙‑碳化硅‑碳复相耐火材料。本发明具有成本低廉和工艺简单的特点；所制备的钛铝酸钙‑碳化硅‑碳复相耐火材料的体积密度较高、抗折耐压强度较大、热膨胀系数较低和热震稳定性优良。

Description

钛铝酸钙-碳化硅-碳复相耐火材料及其制备方法
技术领域
本发明属于高炉出铁沟技术领域。具体涉及一种钛铝酸钙-碳化硅-碳复相耐火材料及其制备方法。
背景技术
随着钢铁行业的不景气、出铁场整体承包价格的降低以及冶炼行业产生的大量废渣的堆积，降低铁钩浇注料的原料成本和对废物进行利用具有重大的意义。当前，高炉出铁沟工作层主要用Al2O3-SiC-C复相耐火材料。以矾土熟料、棕刚玉、球状沥青和碳化硅作为主要原料，用高铝矾土和均化矾土取代棕刚玉，虽然制品的成本降低，但是制品的体密下降、显气孔率上升、常温强度下降和抗侵蚀性能下降（魏建修, 樊海兵等.矾土骨料对Al2O3-SiC-C铁钩浇注料性能的影响[J]. 耐火材料, 2013, 47(4): 274~277.）。以电熔棕刚玉、电熔白刚玉、活性α-Al2O3、球状沥青、碳化硅等为原料，于1450℃保温3h，由于在刚玉颗粒的边缘生成尖晶石层，导致制品的抗渣渗透性较好，但是制品的抗折强度下降，氧化指数增大（韩兵强, 李友胜, 李楠.电熔镁砂加入量对Al2O3-SiC-C浇注料性能的影响[J]. 耐火材料, 2008, 42(1): 10~13.）。“Si3N4加入量对Al2O3-SiC-C铁沟浇注料性能的影响”（李朝云, 涂军波, 魏军从. Si3N4加入量对Al2O3-SiC-C铁沟浇注料性能的影响[J]. 耐火材料,2009, 43(4): 260~262.）一文中以电熔棕刚玉、碳化硅、α-Al2O3、白刚玉、硅灰、硅粉和Si3N4为原料，虽然Si3N4替换球状沥青可以减少环境污染和解决碳的亲水性较差而引起的问题，但是制品的成本上升，且制品需要预先高温处理。
发明内容
本发明旨在克服现有技术缺陷，目的在于提供一种成本低廉和和工艺简单的钛铝酸钙-碳化硅-碳复相耐火材料的制备方法，用该方法制备的钛铝酸钙-碳化硅-碳复相耐火材料的体积密度较高、抗折耐压强度较大、热膨胀系数较低和热震稳定性优良。
为实现上述目的，本发明所采用的技术方案是：以50~60wt%的钛铝酸钙颗粒、5~10wt%的碳化硅颗粒、10~20wt%的碳化硅细粉、5~10wt%的氧化铝微粉、10~20wt%的电熔棕刚玉细粉和2~4wt%的球状沥青为原料，外加所述原料3~4wt%的硅溶胶、0.05~0.2wt%的分散剂和4~6wt%的水，搅拌5~8min，振动成型，室温养护20~28h，90~115℃条件下干燥20~24h，制得钛铝酸钙-碳化硅-碳复相耐火材料。
所述钛铝酸钙颗粒的主要化学成分是：Al2O3≥74.18wt%，CaO≥11.69wt%，TiO2≥11.08wt%，Fe2O3≥1.03wt%，MgO≤1.51wt%，SiO2≤0.42wt%；所述钛铝酸钙颗粒的密度为3.28g/cm3，钛铝酸钙颗粒的粒度≤5mm。
所述碳化硅颗粒的SiC含量≥98.78wt%；碳化硅颗粒的粒度≤3mm。
所述碳化硅细粉的SiC含量≥98.78wt%；碳化硅细粉的粒度≤0.088mm。
所述氧化铝微粉的Al2O3含量≥97.69wt%；氧化铝微粉的粒度≤0.058mm。
所述电熔棕刚玉细粉的Al2O3含量≥95.04wt%；所述电熔棕刚玉细粉的粒度≤0.088mm。
所述球状沥青的C含量≥86.26wt%；球状沥青的粒度≤0.088mm。
所述分散剂为六偏磷酸钠或聚丙烯酸钠。
由于采用上述技术方案，本发明与现有技术相比具有以下优点：
1、本发明采用的原料钛铝酸钙来源丰富，成本低廉，显著地降低了钛铝酸钙-碳化硅-碳复相耐火材料的开发成本。
2、本发明利用钛铝酸钙原料的优良特性，如高的熔点、高的耐火度、较低的热膨胀系数和优良的抗热震性能，提高了钛铝酸钙-碳化硅-碳复相耐火材料的热震稳定性。
3、本发明利用钛铝酸钙的多相性，如钛铝酸钙中的六铝酸钙的片状晶形作为嵌入相有利于铝酸钙-莫来石复相耐火材料强度的提升，又如钛铝酸钙中高熔点的钛酸钙和六铝酸钙可以阻止渣的渗透，显著提高了钛铝酸钙-碳化硅-碳复相耐火材料的抗侵蚀性能。
本发明所制备的钛铝酸钙-碳化硅-碳复相耐火材料经检测：体积密度为2.82~2.87g·cm-3；显气孔率为15~17%；抗折强度为14~16MPa；耐压强度为90~110MPa；热膨胀系数为4.55×10-6~5.05×10-6℃-1 (1400℃)；热震（∆T=1100℃，水冷3次）后强度保持率为50~60%。
因此，本发明具有成本低廉和工艺简单的特点；所制备的钛铝酸钙-碳化硅-碳复相耐火材料的体积密度较高、抗折耐压强度较大、热膨胀系数较低和热震稳定性优良的特点。
具体实施方式
下面结合具体实施方式对本发明作进一步的描述，并非对其保护范围的限制。
为避免重复，先将本具体实施方式所涉及的物料统一描述如下，实施例中不再赘述：
以50~60wt%的钛铝酸钙颗粒、5~10wt%的碳化硅颗粒、10~20wt%的碳化硅细粉、5~10wt%的氧化铝微粉、10~20wt%的电熔棕刚玉细粉和2~4wt%的球状沥青为原料，外加所述原料3~4wt%的硅溶胶、0.05~0.2wt%的分散剂和4~6wt%的水，搅拌5~8min，振动成型，室温养护20~28h，90~115℃条件下干燥20~24h，制得钛铝酸钙-碳化硅-碳复相耐火材料。
所述钛铝酸钙颗粒的主要化学成分是：Al2O3≥74.18wt%，CaO≥11.69wt%，TiO2≥11.08wt%，Fe2O3≥1.03wt%，MgO≤1.51wt%，SiO2≤0.42wt%；所述钛铝酸钙颗粒的密度为3.28g/cm3，钛铝酸钙颗粒的粒度≤5mm。
所述碳化硅颗粒的SiC含量≥98.78wt%；碳化硅颗粒的粒度≤3mm。
所述碳化硅细粉的SiC含量≥98.78wt%；碳化硅细粉的粒度≤0.088mm。
所述氧化铝微粉的Al2O3含量≥97.69wt%；氧化铝微粉的粒度≤0.058mm。
所述电熔棕刚玉细粉的Al2O3含量≥95.04wt%；所述电熔棕刚玉细粉的粒度≤0.088mm。
所述球状沥青的C含量≥86.26wt%；球状沥青的粒度≤0.088mm。
所述分散剂为六偏磷酸钠或聚丙烯酸钠。
由于采用上述技术方案，本发明与现有技术相比具有以下优点：
1、本发明采用的原料钛铝酸钙来源丰富，成本低廉，显著地降低了钛铝酸钙-碳化硅-碳复相耐火材料的开发成本。
2、本发明利用钛铝酸钙原料的优良特性，如高的熔点、高的耐火度、较低的热膨胀系数和优良的抗热震性能，提高了钛铝酸钙-碳化硅-碳复相耐火材料的热震稳定性。
3、本发明利用钛铝酸钙的多相性，如钛铝酸钙中的六铝酸钙的片状晶形作为嵌入相有利于铝酸钙-莫来石复相耐火材料强度的提升，又如钛铝酸钙中高熔点的钛酸钙和六铝酸钙可以阻止渣的渗透，显著提高了钛铝酸钙-碳化硅-碳复相耐火材料的抗侵蚀性能。
本实施例所制备的钛铝酸钙-碳化硅-碳复相耐火材料经检测：体积密度为2.82~2.87g·cm-3；显气孔率为15~17%；抗折强度为14~16MPa；耐压强度为90~110MPa；热膨胀系数为4.55×10-6~5.05×10-6℃-1 (1400℃)；热震（∆T=1100℃，水冷3次）后强度保持率为50~60%。
因此，本发明具有成本低廉和工艺简单的特点；所制备的钛铝酸钙-碳化硅-碳复相耐火材料的体积密度较高、抗折耐压强度较大、热膨胀系数较低和热震稳定性优良的特点。
实施例1
一种钛铝酸钙-碳化硅-碳复相耐火材料及其制备方法。本实施例所述制备方法是：
以50~54wt%的钛铝酸钙颗粒、5~7wt%的碳化硅颗粒、10~14wt%的碳化硅细粉、8~10wt%的氧化铝微粉、16~20wt%的电熔棕刚玉细粉和2~4wt%的球状沥青为原料，外加所述原料3~4wt%的硅溶胶、0.05~0.2wt%的分散剂和4~4.7wt%的水，搅拌5~8min，振动成型，室温养护20~23h，90~115℃条件下干燥20~24h，制得钛铝酸钙-碳化硅-碳复相耐火材料。
所述分散剂为六偏磷酸钠或聚丙烯酸钠。
本实施例所制备的钛铝酸钙-碳化硅-碳复相耐火材料经检测：体积密度为2.85~2.87g·cm-3；显气孔率为15~15.8%；抗折强度为15.2~16MPa；耐压强度为102~110MPa；热膨胀系数为4.85×10-6~5.05×10-6℃-1 (1400℃)；热震（∆T=1100℃，水冷3次）后强度保持率为52~56%。
实施例2
一种钛铝酸钙-碳化硅-碳复相耐火材料及其制备方法。本实施例所述制备方法是：
以52~56wt%的钛铝酸钙颗粒、6~8wt%的碳化硅颗粒、12~16wt%的碳化硅细粉、7~9wt%的氧化铝微粉、14~18wt%的电熔棕刚玉细粉和2~4wt%的球状沥青为原料，外加所述原料3~4wt%的硅溶胶、0.05~0.2wt%的分散剂和4.4~5.1wt%的水，搅拌5~8min，振动成型，室温养护22~24h，90~115℃条件下干燥20~24h，制得钛铝酸钙-碳化硅-碳复相耐火材料。
所述分散剂为六偏磷酸钠或聚丙烯酸钠。
本实施例所制备的钛铝酸钙-碳化硅-碳复相耐火材料经检测：体积密度为2.84~2.86g·cm-3；显气孔率为15.4~16.2%；抗折强度为14.8~15.6MPa；耐压强度为98~104MPa；热膨胀系数为4.75×10-6~4.95×10-6℃-1 (1400℃)；热震（∆T=1100℃，水冷3次）后强度保持率为50~54%。
实施例3
一种钛铝酸钙-碳化硅-碳复相耐火材料及其制备方法。本实施例所述制备方法是：
以54~58wt%的钛铝酸钙颗粒、8~10wt%的碳化硅颗粒、14~18wt%的碳化硅细粉、6~8wt%的氧化铝微粉、12~16wt%的电熔棕刚玉细粉和2~4wt%的球状沥青为原料，外加所述原料3~4wt%的硅溶胶、0.05~0.2wt%的分散剂和4.8~5.5wt%的水，搅拌5~8min，振动成型，室温养护23~26h，90~115℃条件下干燥20~24h，制得钛铝酸钙-碳化硅-碳复相耐火材料。
所述分散剂为六偏磷酸钠或聚丙烯酸钠。
本实施例所制备的钛铝酸钙-碳化硅-碳复相耐火材料经检测：体积密度为2.83~2.85g·cm-3；显气孔率为15.8~16.8%；抗折强度为14.4~15.2MPa；耐压强度为94~100MPa；热膨胀系数为4.65×10-6~4.85×10-6℃-1 (1400℃)；热震（∆T=1100℃，水冷3次）后强度保持率为54~58%。
实施例4
一种钛铝酸钙-碳化硅-碳复相耐火材料及其制备方法。本实施例所述制备方法是：
以56~60wt%的钛铝酸钙颗粒、7~9wt%的碳化硅颗粒、16~20wt%的碳化硅细粉、5~7wt%的氧化铝微粉、10~14wt%的电熔棕刚玉细粉和2~4wt%的球状沥青为原料，外加所述原料3~4wt%的硅溶胶、0.05~0.2wt%的分散剂和5.2~6wt%的水，搅拌5~8min，振动成型，室温养护25~28h，90~115℃条件下干燥20~24h，制得钛铝酸钙-碳化硅-碳复相耐火材料。
所述分散剂为六偏磷酸钠或聚丙烯酸钠。
本实施例所制备的钛铝酸钙-碳化硅-碳复相耐火材料经检测：体积密度为2.82~2.84g·cm-3；显气孔率为15.8~17%；抗折强度为14~14.8MPa；耐压强度为90~96MPa；热膨胀系数为4.55×10-6~4.75×10-6℃-1 (1400℃)；热震（∆T=1100℃，水冷3次）后强度保持率为56~60%。
本具体实施方式与现有技术相比具有以下优点：
1、本具体实施方式采用的原料钛铝酸钙来源丰富，成本低廉，显著地降低了钛铝酸钙-碳化硅-碳复相耐火材料的开发成本。
2、本具体实施方式利用钛铝酸钙原料的优良特性，如高的熔点、高的耐火度、较低的热膨胀系数和优良的抗热震性能，提高了钛铝酸钙-碳化硅-碳复相耐火材料的热震稳定性。
3、本具体实施方式利用钛铝酸钙的多相性，如钛铝酸钙中的六铝酸钙的片状晶形作为嵌入相有利于铝酸钙-莫来石复相耐火材料强度的提升，又如钛铝酸钙中高熔点的钛酸钙和六铝酸钙可以阻止渣的渗透，显著提高了钛铝酸钙-碳化硅-碳复相耐火材料的抗侵蚀性能。
本具体实施方式所制备的钛铝酸钙-碳化硅-碳复相耐火材料经检测：体积密度为2.82~2.87g·cm-3；显气孔率为15~17%；抗折强度为14~16MPa；耐压强度为90~110MPa；热膨胀系数为4.55×10-6~5.05×10-6℃-1 (1400℃)；热震（∆T=1100℃，水冷3次）后强度保持率为50~60%。
因此，本具体实施方式具有成本低廉和工艺简单的特点；所制备的钛铝酸钙-碳化硅-碳复相耐火材料的体积密度较高、抗折耐压强度较大、热膨胀系数较低和热震稳定性优良的特点。

Claims (9)

1.一种钛铝酸钙-碳化硅-碳复相耐火材料的制备方法，其特征在于：以50~60wt%的钛铝酸钙颗粒、5~10wt%的碳化硅颗粒、10~20wt%的碳化硅细粉、5~10wt%的氧化铝微粉、10~20wt%的电熔棕刚玉细粉和2~4wt%的球状沥青为原料，外加所述原料3~4wt%的硅溶胶、0.05~0.2wt%的分散剂和4~6wt%的水，搅拌5~8min，振动成型，室温养护20~28h，90~115℃条件下干燥20~24h，制得钛铝酸钙-碳化硅-碳复相耐火材料。
2.根据权利要求1所述的钛铝酸钙-碳化硅-碳复相耐火材料的制备方法，其特征在于所述钛铝酸钙颗粒的主要化学成分是：Al2O3≥74.18wt%，CaO≥11.69wt%，TiO2≥11.08wt%，Fe2O3≥1.03wt%，MgO≤1.51wt%，SiO2≤0.42wt%；所述钛铝酸钙颗粒的密度为3.28g/cm3，钛铝酸钙颗粒的粒度≤5mm。
3.根据权利要求1所述的钛铝酸钙-碳化硅-碳复相耐火材料的制备方法，其特征在于所述碳化硅颗粒的SiC含量≥98.78wt%；碳化硅颗粒的粒度≤3mm。
4.根据权利要求1所述的钛铝酸钙-碳化硅-碳复相耐火材料的制备方法，其特征在于所述碳化硅细粉的SiC含量≥98.78wt%；碳化硅细粉的粒度≤0.088mm。
5.根据权利要求1所述的钛铝酸钙-碳化硅-碳复相耐火材料的制备方法，其特征在于所述氧化铝微粉的Al2O3含量≥97.69wt%；氧化铝微粉的粒度≤0.058mm。
6.根据权利要求1所述的钛铝酸钙-碳化硅-碳复相耐火材料的制备方法，其特征在于所述电熔棕刚玉细粉的Al2O3含量≥95.04wt%；所述电熔棕刚玉细粉的粒度≤0.088mm。
7.根据权利要求1所述的钛铝酸钙-碳化硅-碳复相耐火材料的制备方法，其特征在于所述球状沥青的C含量≥86.26wt%；球状沥青的粒度≤0.088mm。
8.根据权利要求1所述的钛铝酸钙-碳化硅-碳复相耐火材料的制备方法，其特征在于所述分散剂为六偏磷酸钠或聚丙烯酸钠。
9.一种钛铝酸钙-碳化硅-碳复相耐火材料，其特征在于所述钛铝酸钙-碳化硅-碳复相耐火材料是根据权利要求1~8项中任一项所述的钛铝酸钙-碳化硅-碳复相耐火材料的制备方法所制备的钛铝酸钙-碳化硅-碳复相耐火材料。
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