CN105622121B - 一种高温下陶瓷结合的低碳镁铝碳砖及其制备方法 - Google Patents

一种高温下陶瓷结合的低碳镁铝碳砖及其制备方法 Download PDF

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CN105622121B
CN105622121B CN201610031298.1A CN201610031298A CN105622121B CN 105622121 B CN105622121 B CN 105622121B CN 201610031298 A CN201610031298 A CN 201610031298A CN 105622121 B CN105622121 B CN 105622121B
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罗明
方斌祥
尹明强
马铮
王落霞
喻燕
刘中山
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Zhejiang Zili High Temperature Technology Co., Ltd
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Abstract

本发明公开了一种高温下陶瓷结合的低碳镁铝碳砖及其制备方法,其中制备方法包括如下步骤:将低碳镁铝碳砖中的原料混合均匀后,压制成生坯,然后将生坯置于150~220℃下烘烤6~12h制成;所述低碳镁铝碳砖的原料的重量份组成为:电熔镁砂颗粒40~55份;电熔镁砂细粉10~25份;高铝矾土颗粒10~25份;刚玉细粉5~15份;锆英石颗粒2~4份;锆英石细粉4~8份;鳞片石墨2~4份;金属Al纤维1~2份;单质Si纤维1~2份;结合剂2~4份。本发明公开的低碳镁铝碳砖相对于传统碳结合的低碳镁铝碳砖具有更加优异的中高温强度、抗热震性能和抗氧化性能。

Description

一种高温下陶瓷结合的低碳镁铝碳砖及其制备方法
技术领域
本发明涉及耐火材料技术领域,具体涉及一种高温下陶瓷结合的低碳镁铝碳砖及其制备方法。
背景技术
随着人类生活水平的不断提高,对传统不锈钢的品质提出了更高的要求。众所周知,碳元素是不锈钢中最有害的杂质元素之一,在钢水精炼过程中要求其含量尽可能低,如高纯铁素体等不锈钢要求其中的碳元素含量一般在80ppm以下,有时甚至要求在50ppm以下。
传统不锈钢冶炼过程中所用的电炉母液包、精炼钢包等包底、熔池部位广泛使用C含量大于10%的含碳耐火材料,如镁铝碳砖、镁钙碳砖、镁碳砖等。由于该部位所用耐火材料具有较高的碳含量,在钢水精炼过程中,耐火材料中的碳会向钢水中发生溶解,从而会对钢水产生增碳的问题,参见文献[李楠.钢与耐火材料的作用及耐火材料的选择[J].耐火材料,2006,40:19-22]。因此,为了满足高档不锈钢的冶炼生产,冶炼过程中的各种母液包、精炼钢包等重要容器逐渐开始采用低碳含量耐火材料。
当含碳耐火材料中的碳含量降低后,材料的抗热震稳定性能会大幅度降低,严重影响了材料的使用寿命。因此,为了改善因碳含量降低后带来的热震性问题,国内外研究者广泛采用微纳米结构碳源来取代传统鳞片石墨,来制备低碳碳复合耐火材料,具体列举如下:
如公开号为CN 101475382A的中国发明专利文献公开了一种低碳镁碳砖的制作方法,该方法主要采用粒度为10-100nm的微纳米级鳞片石墨来制备低碳镁碳砖,改善材料的热震性能和抗渣侵蚀性能。但该方法采用纳米级鳞片石墨生产成本高,制作困难,同时存在着反应活性大、容易出现氧化等问题。
如公开号CN101367669A的中国发明专利文献公开了一种含B4C-C复合粉体和纳米TiC粉体的低碳镁碳砖及其制备方法,该方法通过在镁碳砖中引入一定量的纳米炭黑、B4C和TiC复合粉体来制备低碳镁碳砖。但该方法存在纳米炭黑分散困难、反应活性大、容易出现氧化和发生结构蚀变等问题。
如公开号CN103304248A的中国发明专利文献公开了一种低碳镁碳耐火材料及其制备方法,该方法通过在传统镁碳砖中添加碳纳米管,来制备出低碳镁碳砖。但该方法存在碳纳米管成本高、分散困难、且碳纳米管反应活性大、容易出现氧化等问题。
如公开号CN102295464A的中国发明专利文献公开了一种碳复合耐火材料及其制备方法,该方法采用在碳复合耐火材料中引入石墨烯方法制备低碳碳复合耐火材料,来改善材料的热震稳定性能和抗氧化性能。但该方法仍然存在石墨烯成本高、分散困难、且反应活性大、容易出现氧化和发生结构蚀变等问题。
综上所述,为了解决目前不锈钢冶炼过程中,精炼钢包熔池部位用镁铝碳砖、镁碳砖因碳含量太高所带来的对钢水增碳问题,现有技术采用微纳米结构碳源,如微纳米级鳞片石墨、纳米炭黑、碳纳米管和石墨烯等,制备出常温和中高温下都为纳米碳结合的低碳耐火材料,但在生产和使用过程中存在着成本较高、分散困难、且材料在高温使用过程中纳米碳源反应活性大、容易出现氧化和发生结构蚀变等问题。因此,为了提高不锈钢冶炼过程中精炼钢包的使用寿命,有必要对现有技术中采用的内衬材料进行改进。
发明内容
本发明提供了一种高温下陶瓷结合的低碳镁铝碳砖及其制备方法,该低碳镁铝碳砖在中高温使用过程中,材料内部原位形成大量的针状、纤维状的莫来石和橄榄石、以及晶须状的Al4C3和SiC等陶瓷相,使材料内部的结合方式由传统纳米碳结合转变为陶瓷结合,同时,锆英石在高温下分解产生的单斜氧化锆,在材料内部发生相变会产生微裂纹增韧,纤维状、晶须状陶瓷结合相以及相变增韧,赋予本发明所制备的低碳镁铝碳砖相对于传统碳结合的材料具有更加优异的中高温强度、抗热震性能和抗氧化性能。
一种高温下陶瓷结合的低碳镁铝碳砖的制备方法,其特征在于,包括如下步骤:将低碳镁铝碳砖中的原料混合均匀后,压制成生坯,然后将生坯置于150~220℃下烘烤6~12h制成;所述低碳镁铝碳砖的原料的重量份组成为:
本发明在低碳镁铝碳砖中引入锆英石颗粒和锆英石细粉,在高温下使用过程中,锆英石分解成单斜ZrO2和非晶质SiO2相,SiO2在材料内部与刚玉细粉和镁砂细粉反应生成针状、纤维状的莫来石和镁橄榄石陶瓷结合相,赋予材料非常优异的中高温强度和抗热震性能。
同时,单斜氧化锆在材料内部发生相变,产生微裂纹增韧,能够进一步提高低碳镁铝碳砖的热震性能。
本发明在低碳镁铝碳砖中引入金属Al纤维和单质Si纤维,在高温下使用过程中,二者与材料中的鳞片石墨反应生成晶须状的Al4C3、SiC等陶瓷结合相,使所得的低碳镁铝碳砖具有非常优异的中高温强度和抗热震性能。
本发明提供的高温陶瓷结合的低碳镁铝碳砖在埋炭气氛下经1000℃×3h处理后的耐压强度为30~40MPa,抗折强度为4~7MPa;在埋炭气氛下经1600℃×3h处理后的耐压强度为40~50MPa,抗折强度为7~10MPa。在还原气氛中于1400℃×0.5h下的高温抗折强度为18~24MPa。
抗热震实验表明:在1100℃水冷条件下热震1次后的强度保持率为80~90%,热震2次后的强度保持率为70~80%,热震3次后的强度保持率为60~70%,热震4次后的强度保持率为55~60%。
抗氧化实验表明:1000℃×3h空气条件下氧化失重率为3.5%~4.5%,氧化层厚度为2.0~3.0mm;1400℃×3h空气条件下氧化失重率为5.5~6.5%,氧化层厚度为4.0~5.0mm。
作为优选,所述低碳镁铝碳砖的原料的重量份组成为:
作为优选,所述电熔镁砂颗粒和电熔镁砂细粉的化学成分及质量百分含量为:MgO≥97.0wt%,CaO≤1.8wt%,SiO2≤0.9wt%;
所述电熔镁砂颗粒的粒度级配为:
5~3mm 10~15份;
2.999~1mm 10~15份;
0.999~0.089mm 20~25份;
所述电熔镁砂细粉的粒度级配为:
0.088~0.045mm 5~10份;
<0.045mm 5~15份。
作为优选,所述高铝矾土颗粒的化学成分及质量百分含量为:Al2O3≥82.0wt%,SiO2≤12.0wt%,TiO2≤6.0wt%,K2O+Na2O≤0.6wt%;
所述高铝矾土颗粒的粒度级配为:
2.999~1mm 5~10份;
0.999~0.089mm 5~15份。
作为优选,所述刚玉细粉为电熔棕刚玉细粉或板状刚玉细粉中的一种,其中电熔棕刚玉细粉的化学成分及质量百分含量为:Al2O3≥93.0wt%,TiO2≤3.0wt%;板状刚玉细粉的化学成分及质量百分含量为Al2O3≥99.0wt%;所述刚玉细粉的粒度<0.088mm。
作为优选,所述锆英石颗粒和锆英石细粉的化学成分及质量百分含量为:ZrO2≥60.0wt%,SiO2≤40.0%;所述锆英石颗粒的粒度为0.999~0.089mm;
所述锆英石细粉的粒度级配为:
0.088~0.045mm 2~4份;
<0.045mm 2~4份。
作为优选,所述鳞片石墨的化学成分及质量百分含量为C≥94.0%,粒度为<0.088mm。
作为优选,所述金属Al纤维的化学组成及质量百分含量为Al>97.0%,直径为20~200μm,长度为0.2~2mm。
作为优选,所述单质Si纤维的化学组成及质量百分含量为Si>97.0%,直径为20~200μm,长度为0.2~2mm。
作为优选,所述结合剂为木质素溶液、磷酸二氢铝溶液、热固性酚醛树脂中的一种。
本发明还提供了一种低碳镁铝碳砖,采用所述的制备方法制得。
与现有技术相比,本发明具有以下有益效果:
在高温使用过程中材料内部形成的针状、纤维状的莫来石和镁橄榄石以及晶须状的Al4C3、SiC等陶瓷结合相,赋予材料非常优异的中高温强度和抗热震性能。同时,材料内部锆英石分解形成的单斜氧化锆,在使用过程中会产生相变形成微裂纹增韧的方式,进一步提高了低碳镁铝碳砖的热震性能。
与传统采用纳米碳结合的低碳耐火材料(低碳镁铝碳砖、低碳镁碳砖等)相比,本发明所制备的低碳镁铝碳砖生产工艺制作简单、原料成本较低,且有效避免了在材料制备和使用过程中纳米碳存在的分散困难、反应活性高和容易氧化的问题,能够大幅度提高材料的中高温强度、热震稳定性能和抗氧化性能。
具体实施方式
下面结合具体实施例1~5以及对比例对本发明进行进一步的描述。
实施例1~5
各实施例中低碳镁铝碳砖的制备方法如下:
先将电熔镁砂颗粒、高铝矾土颗粒、锆英石颗粒干混3分钟,加入结合剂湿混4分钟,再加入鳞片石墨混碾8分钟,最后加入电熔镁砂细粉、刚玉细粉、锆英石细粉、金属Al纤维和单质Si纤维混碾12分钟,经困料,压制成生胚,然后于干燥窑中经200℃处理10h制得。
实施例1~5的原料重量份组成见表1,实施例1~5制备获得的低碳镁铝碳砖性能测试结果见表2。
表1
表1中所用的电熔镁砂颗粒和电熔镁砂细粉的化学成分及质量百分含量为:MgO≥97.0wt%,CaO≤1.8wt%,SiO2≤0.9wt%。
表1中所用的高铝矾土颗粒的化学成分及其百分含量为:Al2O3≥82.0wt%,SiO2≤12.0wt%,TiO2≤6.0wt%,K2O+Na2O≤0.6wt%。
表1中,实施例1~3采用电熔棕刚玉细粉,实施例4~5以及对比例1采用板状刚玉细粉,电熔棕刚玉细粉的化学成分及质量百分含量为:Al2O3≥93.0wt%,TiO2≤3.0wt%;板状刚玉细粉的化学成分及质量百分含量为Al2O3≥99.0wt%。
表1中所用的锆英石颗粒和锆英石细粉的化学成分及质量百分含量为:ZrO2≥60.0wt%,SiO2≤40.0%。
表1中所用的鳞片石墨的化学成分及其百分含量为C≥94.0%,粒度为<0.15mm。
表1中所用的金属Al纤维的化学组成及百分含量为Al>97.0%,直径为20μm,长度为0.2~2mm;所用的单质Si纤维的化学组成及百分含量为Si>97.0%,直径为20μm,长度为0.2~2mm。
对比例1
对比例1的制备方法同实施例1,对比例1的原料重量份组成如表1所示。
对比例1制备获得的低碳镁铝碳砖的性能测试结果如表2所示。
对比例1中所用的纳米炭黑的化学组成及百分含量为C>98.0%,粒度为<100nm。
对比例1中所用B4C抗氧化剂的化学组成及百分含量为B4C>98.0%,粒度为<0.045mm。
实施例1~5以及对比例1中结合剂的使用份数均为3份。
表2
由表2可以看出,本发明制备的低碳镁铝碳砖,相比现有的采用纳米炭黑结合的低碳镁铝碳砖,具有中高温强度大、抗热震性能和抗氧化性能更加优异的优点,应用于精炼钢包熔池部位能够大幅度提高其使用寿命。

Claims (10)

1.一种高温下陶瓷结合的低碳镁铝碳砖的制备方法,其特征在于,包括如下步骤:将低碳镁铝碳砖中的原料混合均匀后,压制成生坯,然后将生坯置于150~220℃下烘烤6~12h制成;所述低碳镁铝碳砖的原料的重量份组成为:
2.如权利要求1所述的高温下陶瓷结合的低碳镁铝碳砖的制备方法,其特征在于,所述电熔镁砂颗粒和电熔镁砂细粉的化学成分及质量百分含量为:MgO≥97.0wt%,CaO≤1.8wt%,SiO2≤0.9wt%;
所述电熔镁砂颗粒的粒度级配为:
5~3mm 10~15份;
2.999~1mm 10~15份;
0.999~0.089mm 20~25份;
所述电熔镁砂细粉的粒度级配为:
0.088~0.045mm 5~10份;
<0.045mm 5~15份。
3.如权利要求1所述的高温下陶瓷结合的低碳镁铝碳砖的制备方法,其特征在于,所述高铝矾土颗粒的化学成分及质量百分含量为:Al2O3≥82.0wt%,SiO2≤12.0wt%,TiO2≤6.0wt%,K2O+Na2O≤0.6wt%;
所述高铝矾土颗粒的粒度级配为:
2.999~1mm 5~10份;
0.999~0.089mm 5~15份。
4.如权利要求1所述的高温下陶瓷结合的低碳镁铝碳砖的制备方法,其特征在于,所述刚玉细粉为电熔棕刚玉细粉或板状刚玉细粉中的一种,其中电熔棕刚玉细粉的化学成分及质量百分含量为:Al2O3≥93.0wt%,TiO2≤3.0wt%;板状刚玉细粉的化学成分及质量百分含量为Al2O3≥99.0wt%;所述刚玉细粉的粒度<0.088mm。
5.如权利要求1所述的高温下陶瓷结合的低碳镁铝碳砖的制备方法,其特征在于,所述锆英石颗粒和锆英石细粉的化学成分及质量百分含量为:ZrO2≥60.0wt%,SiO2≤40.0%;所述锆英石颗粒的粒度为0.999~0.089mm;
所述锆英石细粉的粒度级配为:
0.088~0.045mm 2~4份;
<0.045mm 2~4份。
6.如权利要求1所述的高温下陶瓷结合的低碳镁铝碳砖的制备方法,其特征在于,所述鳞片石墨的化学成分及质量百分含量为C≥94.0%,粒度为<0.088mm。
7.如权利要求1所述的高温下陶瓷结合的低碳镁铝碳砖的制备方法,其特征在于,所述金属Al纤维的化学组成及质量百分含量为Al>97.0%,直径为20~200μm,长度为0.2~2mm。
8.如权利要求1所述的高温下陶瓷结合的低碳镁铝碳砖的制备方法,其特征在于,所述单质Si纤维的化学组成及质量百分含量为Si>97.0%,直径为20~200μm,长度为0.2~2mm。
9.如权利要求1所述的高温下陶瓷结合的低碳镁铝碳砖的制备方法,其特征在于,所述结合剂为木质素溶液、磷酸二氢铝溶液、热固性酚醛树脂中的一种。
10.一种低碳镁铝碳砖,其特征在于,采用如权利要求1~9任一项所述的制备方法制得。
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