CN107954710B - 一种碳化硅结合钛铝酸钙复相耐火材料及其制备方法 - Google Patents
一种碳化硅结合钛铝酸钙复相耐火材料及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种碳化硅结合钛铝酸钙复相耐火材料及其制备方法。其技术方案是:将50~55wt%的钛铝酸钙颗粒、15~20wt%的钛铝酸钙细粉、10~15wt%的单质硅粉、1~3wt%的氧化硼细粉和10~20wt%的热固性酚醛树脂混合,混辗8~10min,于130~150MPa条件下机压成型,在90~110℃条件下干燥20~30小时,得到干燥后的坯体。将干燥后的坯体置于底部铺有焦炭的氧化铝匣钵中,然后在所述氧化铝匣钵中铺满焦炭,再于1400~1450℃条件下保温2~3小时,随炉冷却,制得碳化硅结合钛铝酸钙复相耐火材料。本发明具有成本低廉、工艺简单和成品率高的特点;所制制品体积密度较大、抗折耐压强度大、导热系数小、常温耐磨性好和抗热震性能优良。
Description
技术领域
本发明属于钛铝酸钙复相耐火材料技术领域。具体涉及一种碳化硅结合钛铝酸钙复相耐火材料及其制备方法。
背景技术
当前,对冶炼各种合金产生的废渣进行一系列工艺处理后得到一种优质的复相耐火原料具有重要的意义。水泥回转窑过渡带用矾土-碳化硅复相耐火材料具有优良的抗热震性、高的强度和好的耐磨性,但是该材料中致密特级矾土骨料和碳化硅骨料的比例占据很大,虽提高了材料的导热系数,但不利于节能环保(刘振英,姚峰.水泥窑用特种硅莫砖的研制及应用[J].硅酸盐通报,2012,31(1):128~131.)(徐平坤.硅莫砖的技术性能及其在水泥回转窑的应用[J].新世纪水泥导报,2010,6:51~55.)。此外,“一种莫来石碳化硅复相耐火材料及其制备方法”(CN106167411A)专利技术,采用涂层包覆轻质莫来石骨料、涂层包覆碳化硅骨料、特级矾土细粉、红柱石细粉等作为原料制备莫来石碳化硅复相耐火材料,虽然材料的导热系数较小,利于节能保温,但是体系中高的Si含量导致的液相以及轻质莫来石骨料导致低的体积密度不利于提高材料的耐火度和耐磨性;另外,莫来石和碳化硅在高温下的体积膨胀的失配也不利于材料的致密化。
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、工艺简单和成品率高的碳化硅结合钛铝酸钙复相耐火材料的制备方法,用该方法制备的碳化硅结合钛铝酸钙复相耐火材料体积密度较大、抗折耐压强度大、导热系数小、常温耐磨性好和抗热震性能优良。
为实现上述目的,本发明所采用的技术方案是:将50~55wt%的钛铝酸钙颗粒、15~20wt%的钛铝酸钙细粉、10~15wt%的单质硅粉、1~3wt%的氧化硼细粉和10~20wt%的热固性酚醛树脂混合,混辗8~10min,得到混合料。将所述混合料于130~150MPa条件下机压成型,在90~110℃条件下干燥20~30小时,得到干燥后的坯体。
将干燥后的坯体置于底部铺有焦炭的氧化铝匣钵中,然后在所述氧化铝匣钵中铺满焦炭,再于1400~1450℃条件下保温2~3小时,随炉冷却,制得碳化硅结合钛铝酸钙复相耐火材料。
所述钛铝酸钙的主要化学成分是:Al2O3≥74.18wt%,CaO≥11.69wt%,TiO2≥11.08wt%。
所述钛铝酸钙颗粒的密度为3.28g/cm3,粒度为≤3mm。
所述钛铝酸钙细粉的粒度为≤0.088mm。
所述单质硅粉的Si含量≥95.9wt%;所述单质硅粉的粒度≤0.088mm。
所述氧化硼细粉的B2O3含量≥98.67wt%;所述氧化硼细粉的粒度≤0.058mm。
由于采用上述技术方案,本发明与现有技术相比具有以下积极效果:
1、本发明所采用的主要原料钛铝酸钙为冶炼钛铁合金的废渣,不仅来源丰富和成本低廉,且制备该原料的工艺简单,故制备碳化硅结合钛铝酸钙复相耐火材料的成本低廉和工艺简单。
2、本发明所用的钛铝酸钙原料的主要物相是CA6、CA2和CaTiO3,具有高的耐磨性、高的熔点、低的热膨胀系数和导热系数、优良的抗热震性和高的高的耐火度。
3、本发明所制备的碳化硅结合钛铝酸钙复相耐火材料是在还原性气氛下烧成,能有效避免钛铝酸钙中的CA6和CA2与单质硅粉氧化得到的SiO2反应所生成的低熔相钙长石,从而保留钛铝酸钙中大部分的CA6、CaTiO3等物相;CA6片状晶形能很好地降低碳化硅结合钛铝酸钙复相耐火材料的导热系数和热膨胀系数。
4、热固性酚醛树脂高温热解形成的碳链会与材料中的单质硅原位反应生成的碳化硅晶须能显著提高碳化硅结合钛铝酸钙复相耐火材料的强度和抗热震性。
本发明所制备的碳化硅结合钛铝酸钙复相耐火材料经检测:成品率为99.0%~99.7%;体积密度为2.76~2.81g·cm-3;显气孔率为14~19%;抗折强度为24~30MPa;耐压强度为90~130MPa;导热系数为1.55~1.65W·m-1·K-1(1000℃);常温耐磨为2.2~2.7cm3;热震(ΔT=1100℃,风冷3次)后强度保持率为80~90%。
因此,本发明具有成本低廉、工艺简单和成品率高的特点;所制备的碳化硅结合钛铝酸钙复相耐火材料具有体积密度较大、抗折耐压强度大、导热系数小、常温耐磨性好和抗热震性能优良。
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:
所述钛铝酸钙的主要化学成分是:Al2O3≥74.18wt%,CaO≥11.69wt%,
TiO2≥11.08wt%。
所述钛铝酸钙颗粒的密度为3.28g/cm3,粒度为≤3mm。
所述钛铝酸钙细粉的粒度为≤0.088mm。
所述单质硅粉的Si含量≥95.9wt%;所述单质硅粉的粒度≤0.088mm。
所述氧化硼细粉的B2O3含量≥98.67wt%;所述氧化硼细粉的粒度≤0.058mm。
实施例1
一种碳化硅结合钛铝酸钙复相耐火材料及其制备方法。本实施例所述制备方法:
将50~52wt%的钛铝酸钙颗粒、15~17wt%的钛铝酸钙细粉、10~12wt%的单质硅粉、1~3wt%的氧化硼细粉和16~20wt%的热固性酚醛树脂混合,混辗8~10min,得到混合料。将所述混合料于130~150MPa条件下机压成型,在90~110℃条件下干燥20~30小时,得到干燥后的坯体。
将干燥后的坯体置于底部铺有焦炭的氧化铝匣钵中,然后在所述氧化铝匣钵中铺满焦炭,再于1400~1450℃条件下保温2~3小时,随炉冷却,制得碳化硅结合钛铝酸钙复相耐火材料。
本实施例所制备的碳化硅结合钛铝酸钙复相耐火材料经检测:成品率为99.0%~99.7%;体积密度为2.79~2.81g·cm-3;显气孔率为17~19%;抗折强度为24~25MPa;耐压强度为90~105MPa;导热系数为1.57~1.61W·m-1·K-1(1000℃);常温耐磨为2.4~2.6cm3;热震(ΔT=1100℃,风冷3次)后强度保持率为84~88%。
实施例2
一种碳化硅结合钛铝酸钙复相耐火材料及其制备方法。本实施例所述制备方法:
将51~53wt%的钛铝酸钙颗粒、16~18wt%的钛铝酸钙细粉、11~13wt%的单质硅粉、1~3wt%的氧化硼细粉和14~18wt%的热固性酚醛树脂混合,混辗8~10min,得到混合料。将所述混合料于130~150MPa条件下机压成型,在90~110℃条件下干燥20~30小时,得到干燥后的坯体。
将干燥后的坯体置于底部铺有焦炭的氧化铝匣钵中,然后在所述氧化铝匣钵中铺满焦炭,再于1400~1450℃条件下保温2~3小时,随炉冷却,制得碳化硅结合钛铝酸钙复相耐火材料。
本实施例所制备的碳化硅结合钛铝酸钙复相耐火材料经检测:成品率为99.0%~99.7%;体积密度为2.78~2.80g·cm-3;显气孔率为16~18%;抗折强度为28~30MPa;耐压强度为115~130MPa;导热系数为1.55~1.59W·m-1·K-1(1000℃);常温耐磨为2.5~2.7cm3;热震(ΔT=1100℃,风冷3次)后强度保持率为86~90%。
实施例3
一种碳化硅结合钛铝酸钙复相耐火材料及其制备方法。本实施例所述制备方法:
将52~54wt%的钛铝酸钙颗粒、17~19wt%的钛铝酸钙细粉、12~14wt%的单质硅粉、1~3wt%的氧化硼细粉和12~16wt%的热固性酚醛树脂混合,混辗8~10min,得到混合料。将所述混合料于130~150MPa条件下机压成型,在90~110℃条件下干燥20~30小时,得到干燥后的坯体。
将干燥后的坯体置于底部铺有焦炭的氧化铝匣钵中,然后在所述氧化铝匣钵中铺满焦炭,再于1400~1450℃条件下保温2~3小时,随炉冷却,制得碳化硅结合钛铝酸钙复相耐火材料。
本实施例所制备的碳化硅结合钛铝酸钙复相耐火材料经检测:成品率为99.0%~99.7%;体积密度为2.77~2.79g·cm-3;显气孔率为15~17%;抗折强度为27~28MPa;耐压强度为105~120MPa;导热系数为1.59~1.63W·m-1·K-1(1000℃);常温耐磨为2.3~2.5cm3;热震(ΔT=1100℃,风冷3次)后强度保持率为82~86%。
实施例4
一种碳化硅结合钛铝酸钙复相耐火材料及其制备方法。本实施例所述制备方法:
将53~55wt%的钛铝酸钙颗粒、18~20wt%的钛铝酸钙细粉、13~15wt%的单质硅粉、1~3wt%的氧化硼细粉和10~14wt%的热固性酚醛树脂混合,混辗8~10min,得到混合料。将所述混合料于130~150MPa条件下机压成型,在90~110℃条件下干燥20~30小时,得到干燥后的坯体。
将干燥后的坯体置于底部铺有焦炭的氧化铝匣钵中,然后在所述氧化铝匣钵中铺满焦炭,再于1400~1450℃条件下保温2~3小时,随炉冷却,制得碳化硅结合钛铝酸钙复相耐火材料。
本实施例所制备的碳化硅结合钛铝酸钙复相耐火材料经检测:成品率为99.0%~99.7%;体积密度为2.76~2.78g·cm-3;显气孔率为14~16%;抗折强度为25~27MPa;耐压强度为100~115MPa;导热系数为1.61~1.65W·m-1·K-1(1000℃);常温耐磨为2.2~2.4cm3;热震(ΔT=1100℃,风冷3次)后强度保持率为80~84%。
本具体实施方式与现有技术相比具有以下积极效果:
1、本具体实施方式所采用的主要原料钛铝酸钙为冶炼钛铁合金的废渣,不仅来源丰富和成本低廉,且制备该原料的工艺简单,故制备碳化硅结合钛铝酸钙复相耐火材料的成本低廉和工艺简单。
2、本具体实施方式所用的钛铝酸钙原料的主要物相是CA6、CA2和CaTiO3,具有高的耐磨性、高的熔点、低的热膨胀系数和导热系数、优良的抗热震性和高的高的耐火度。
3、本具体实施方式所制备的碳化硅结合钛铝酸钙复相耐火材料是在还原性气氛下烧成,能有效避免钛铝酸钙中的CA6和CA2与单质硅粉氧化得到的SiO2反应所生成的低熔相钙长石,从而保留钛铝酸钙中大部分的CA6、CaTiO3等物相;CA6片状晶形能很好地降低碳化硅结合钛铝酸钙复相耐火材料的导热系数和热膨胀系数。
4、热固性酚醛树脂高温热解形成的碳链会与材料中的单质硅原位反应生成的碳化硅晶须能显著提高碳化硅结合钛铝酸钙复相耐火材料的强度和抗热震性。
本具体实施方式所制备的碳化硅结合钛铝酸钙复相耐火材料经检测:成品率为99.0%~99.7%;体积密度为2.76~2.81g·cm-3;显气孔率为14~19%;抗折强度为24~30MPa;耐压强度为90~130MPa;导热系数为1.55~1.65W·m-1·K-1(1000℃);常温耐磨为2.2~2.7cm3;热震(ΔT=1100℃,风冷3次)后强度保持率为80~90%。
因此,本具体实施方式具有成本低廉、工艺简单和成品率高的特点;所制备的碳化硅结合钛铝酸钙复相耐火材料具有体积密度较大、抗折耐压强度大、导热系数小、常温耐磨性好和抗热震性能优良。
Claims (5)
1.一种碳化硅结合钛铝酸钙复相耐火材料的制备方法,其特征在于:将50~55wt%的钛铝酸钙颗粒、15~20wt%的钛铝酸钙细粉、10~15wt%的单质硅粉、1~3wt%的氧化硼细粉和10~20wt%的热固性酚醛树脂混合,混辗8~10min,得到混合料;将所述混合料于130~150MPa条件下机压成型,在90~110℃条件下干燥20~30小时,得到干燥后的坯体;
将干燥后的坯体置于底部铺有焦炭的氧化铝匣钵中,然后在所述氧化铝匣钵中铺满焦炭,再于1400~1450℃条件下保温2~3小时,随炉冷却,制得碳化硅结合钛铝酸钙复相耐火材料;
所述钛铝酸钙颗粒的密度为3.28g/cm3,钛铝酸钙颗粒的粒度为≤3mm;
所述钛铝酸钙细粉的粒度为≤0.088mm;
所述单质硅粉的粒度≤0.088mm;
所述氧化硼细粉的粒度≤0.058mm。
2.根据权利要求1所述的碳化硅结合钛铝酸钙复相耐火材料的制备方法,其特征在于所述钛铝酸钙的主要化学成分是:Al2O3≥74.18wt%,CaO≥11.69wt%,TiO2≥11.08wt%。
3.根据权利要求1所述的碳化硅结合钛铝酸钙复相耐火材料的制备方法,其特征在于所述单质硅粉的Si含量≥95.9wt%。
4.根据权利要求1所述的碳化硅结合钛铝酸钙复相耐火材料的制备方法,其特征在于所述氧化硼细粉的B2O3含量≥98.67wt%。
5.一种碳化硅结合钛铝酸钙复相耐火材料,其特征在于所述碳化硅结合钛铝酸钙复相耐火材料是根据权利要求1~4项中任一项所述的碳化硅结合钛铝酸钙复相耐火材料的制备方法所制备的碳化硅结合钛铝酸钙复相耐火材料。
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