CN109293376B - 一种氮化硅氮化钛结合碳化硅耐火材料及其制备方法 - Google Patents
一种氮化硅氮化钛结合碳化硅耐火材料及其制备方法 Download PDFInfo
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Abstract
本发明具体涉及一种氮化硅氮化钛结合碳化硅耐火材料及其制备方法。其技术方案是:先以55~75wt%的碳化硅颗粒、5~30wt%的碳化硅细粉、5~30wt%的硅粉,0.1~20wt%的钛硅铁合金粉、0~2wt%的石墨和0~2wt%的碳黑为原料,外加所述原料3~8wt%的结合剂,再于混碾机中混练,困料,成型,干燥;然后在含氮气氛中热处理,制得氮化硅氮化钛结合碳化硅耐火材料。所述石墨和碳黑的质量百分含量不同时为0。所述热处理是:先升温至800~1000℃,保温0~12h;再升温至1020~1300℃,保温0.5~12h;然后升温至1320~1450℃,保温0.5~12h。本发明生产成本低,所制制品具有结构均匀致密、抗氧化性能优良、高温力学性能优异、抗热震性能好和抗渣蚀性强的特点。
Description
技术领域
本发明属于碳化硅耐火材料技术领域。具体涉及一种氮化硅氮化钛结合碳化硅耐火材料及其制备方法。
背景技术
氮化硅结合碳化硅制品具有耐高温、耐腐蚀、耐磨损、抗冲刷、抗氧化等优异性能,且对除氢氟酸外的无机酸具有较好的抗侵蚀性,不被金属熔体尤其是非铁金属熔体润湿,耐金属熔体侵蚀,目前已广泛应用于陶瓷、冶金、化工、垃圾焚烧炉等高温工业。但是,由于氮化硅和碳化硅均为共价键化合物,氮化硅/碳化硅陶瓷制品烧结困难,只能在很高温度下获得致密的高性能陶瓷材料,或通过选择各种各样的烧结助剂和添加剂、或采用特殊的烧结工艺来获得致密的高性能陶瓷材料。
反应烧结制备氮化硅结合碳化硅与其它制备方法相比,是一个近净尺寸过程,且工艺简单和参数易于控制,可以制备形状复杂的陶瓷构件,具有广阔的应用前景。该方法是利用硅粉在氮气气氛下发生氮化反应,靠反应生成的氮化硅网络包裹碳化硅颗粒,形成交织结构。由于硅粉转化成氮化硅后体积增加约22%,能够填补坯体颗粒间孔隙,形成新的桥联结构而实现烧结。然而,通过该方法制备的材料有一个共同的缺点,即所获得的材料显气孔率较高,对其抗侵蚀和抗氧化性能有明显影响,在很多情况下不能满足实际使用要求,阻碍了这类材料其它优异性能的发挥。
发明内容
本发明旨在克服现有技术缺陷,提供一种生产成本低的氮化硅氮化钛结合碳化硅耐火材料的制备方法,所制备的氮化硅氮化钛结合碳化硅耐火材料结构均匀致密、抗氧化性能优良、高温力学性能优异、抗热震性能好和抗渣蚀性强。
为实现上述目的,本发明采用的技术方案是:先以55~75wt%的碳化硅颗粒、5~30wt%的碳化硅细粉、5~30wt%的硅粉,0.1~20wt%的钛硅铁合金粉、0~2wt%的石墨和0~2wt%的碳黑为原料,外加所述原料3~8wt%的结合剂,再于混碾机中混练,困料,成型,干燥;然后在含氮气氛中进行热处理,制得氮化硅氮化钛结合碳化硅耐火材料。
所述石墨的质量百分含量和所述碳黑的质量百分含量不同时为0。
所述钛硅铁合金的制备方法是:先向含钛高炉渣中加入占所述含钛高炉渣0~50wt%的碳、0~40wt%的铝、0~40wt%的铁和0~20wt%的镁;混合均匀后进行熔融还原,制得钛硅铁合金;所述碳、铝和镁的质量百分含量不同时为0。
所述热处理的升温制度是:先升温至800~1000℃,保温0~12h;再升温至1020~1300℃,保温0.5~12h;然后升温至1320~1450℃,保温0.5~12h。
所述碳化硅颗粒的SiC含量≥96wt%;所述碳化硅颗粒的粒度为0.088~5mm。
所述碳化硅细粉的SiC含量≥96wt%;所述碳化硅细粉的粒度≤0.088mm。
所述硅粉的Si含量≥95wt%,粒度≤0.088mm。
所述钛硅铁合金粉的粒度≤0.088mm。
所述结合剂为沥青、酚醛树脂、聚乙烯醇、淀粉、羟丙基甲基纤维素和羧甲基纤维素中的一种。
所述含氮气氛为埋碳气氛、或为氨气气氛、或为氮气气氛、或为氮气与氢气的混合气氛。
所述的含钛高炉渣为以钒钛磁铁矿为主要原料经高炉冶炼产生的冷态或热态含钛高炉渣;含钛高炉渣的TiO2含量为12~30wt%。
由于采用上述技术方案,本发明与现有技术相比具有如下积极效果:
本发明在原料中引入钛硅铁合金和碳材料,在氮化反应过程中,钛硅铁合金除形成Si3N4外,还能形成TiN和SiC等,TiN晶粒呈弥散分布,能起到弥散强化的作用。同时,钛硅铁合金中的Ti5Si3、TiSi2和TiFeSi2等合金相在氮化后的体积膨胀分别为44.7%、65.2%和56.7%,较Si粉氮化过程的体积膨胀(23.5%)更大,能进一步促进制品的致密化,从而进一步提高制品的力学性能,改善制品的抗氧化和抗渣性能。钛硅铁合金的引入还能促进SiC和Si3N4晶须的形成及生长,有助于形成晶须结合,从而提高制品的力学性能。此外,TiN导热性能较好,也有助于提高制品的抗热震性能。
本发明以提取自含钛高炉渣的钛硅铁合金为原料,制得氮化硅氮化钛结合碳化硅耐火材料,对钛硅铁合金的高附加值利用具有重要意义,也可以进一步拓宽含钛高炉渣的高附加值利用途径,降低氮化硅氮化钛结合碳化硅耐火材料的生产成本。
本发明制备的氮化硅氮化钛结合碳化硅耐火材料相比于氮化硅结合碳化硅耐火材料的显气孔率下降约20%;耐压强度也大幅度提高。
因此,本发明生产成本低,制得的氮化硅氮化钛结合碳化硅耐火材料具有结构均匀致密、抗氧化性能优良、高温力学性能优异、抗热震性能好和抗渣蚀性强的特点。
附图说明
图1为本发明制备的一种氮化硅氮化钛结合碳化硅耐火材料的XRD图谱;
图2为图1所示氮化硅氮化钛结合碳化硅耐火材料的显微结构图;
图3为本发明制备的另一种氮化硅氮化钛结合碳化硅耐火材料的显微结构图。
具体实施方式
为了更好的理解本发明,下面通过附图和实施例进一步阐述本发明的内容,但本发明不仅仅局限于下面的实施例。
为避免重复,先将本具体实施方式所涉及的技术参数统一描述如下,实施例中不再赘述:
所述碳化硅颗粒的SiC含量≥96wt%;所述碳化硅颗粒的粒度为0.088~5mm。
所述碳化硅细粉的SiC含量≥96wt%;所述碳化硅细粉的粒度≤0.088mm。
所述硅粉的Si含量≥95wt%,粒度≤0.088mm。
所述钛硅铁合金的制备方法是:先向含钛高炉渣中加入占所述含钛高炉渣0~50wt%的碳、0~40wt%的铝、0~40wt%的铁和0~20wt%的镁;混合均匀后进行熔融还原,制得钛硅铁合金;所述碳、铝和镁的质量百分含量不同时为0。
所述钛硅铁合金粉的粒度≤0.088mm。
所述的含钛高炉渣为以钒钛磁铁矿为主要原料经高炉冶炼产生的冷态或热态含钛高炉渣;含钛高炉渣的TiO2含量为12~30wt%。
实施例1
一种氮化硅氮化钛结合碳化硅耐火材料及其制备方法。本实施例所述制备方法是:
先以55~63wt%的碳化硅颗粒、19~30wt%的碳化硅细粉、5~14wt%的硅粉,9.5~20wt%的钛硅铁合金粉和0.1~1.1wt%的碳黑为原料,外加所述原料3~5wt%的结合剂,再于混碾机中混练,困料,成型,干燥,然后在含氮气氛中进行热处理,制得氮化硅氮化钛结合碳化硅耐火材料。
所述热处理的升温制度是:先升温至1020~1300℃,保温0.5~12h;然后升温至1320~1450℃,保温0.5~12h。
所述结合剂为沥青;
所述含氮气氛为埋碳气氛。
实施例2
一种氮化硅氮化钛结合碳化硅耐火材料及其制备方法。本实施例所述制备方法除下述外其余同实施例1:
所述结合剂为酚醛树脂;
所述含氮气氛为氨气气氛。
实施例3
一种氮化硅氮化钛结合碳化硅耐火材料及其制备方法。本实施例所述制备方法除下述外其余同实施例1:
所述结合剂为聚乙烯醇;
所述含氮气氛为氮气气氛。
实施例4
一种氮化硅氮化钛结合碳化硅耐火材料及其制备方法。本实施例所述制备方法除下述外其余同实施例1:
所述结合剂为淀粉;
所述含氮气氛为氮气与氢气的混合气氛。
实施例5
一种氮化硅氮化钛结合碳化硅耐火材料及其制备方法。本实施例所述制备方法除下述外其余同实施例1:
所述结合剂为羟丙基甲基纤维素;
所述含氮气氛为埋碳气氛。
实施例6
一种氮化硅氮化钛结合碳化硅耐火材料及其制备方法。本实施例所述制备方法除下述外其余同实施例1:
所述结合剂为和羧甲基纤维素;
所述含氮气氛为为氨气气氛。
实施例7
一种氮化硅氮化钛结合碳化硅耐火材料及其制备方法。本实施例所述制备方法是:
先以59~68wt%的碳化硅颗粒、7~20wt%的碳化硅细粉、19~30wt%的硅粉,0.1~5wt%的钛硅铁合金粉和0.1~1.1wt%的石墨为原料,外加所述原料4~7wt%的结合剂,再于混碾机中混练,困料,成型,干燥;然后在含氮气氛中进行热处理,制得氮化硅氮化钛结合碳化硅耐火材料。
所述热处理的升温制度是:先升温至800~1000℃,保温0.5~6h;再升温至1020~1300℃,保温6~12h,然后升温至1320~1450℃,保温0.5~8h。
所述结合剂为沥青;
所述含氮气氛为埋碳气氛。
实施例8
一种氮化硅氮化钛结合碳化硅耐火材料及其制备方法。本实施例所述制备方法除下述外其余同实施例7:
所述结合剂为酚醛树脂;
所述含氮气氛为氨气气氛。
实施例9
一种氮化硅氮化钛结合碳化硅耐火材料及其制备方法。本实施例所述制备方法除下述外其余同实施例7:
所述结合剂为聚乙烯醇;
所述含氮气氛为氮气气氛。
实施例10
一种氮化硅氮化钛结合碳化硅耐火材料及其制备方法。本实施例所述制备方法除下述外其余同实施例7:
所述结合剂为淀粉;
所述含氮气氛为氮气与氢气的混合气氛。
实施例11
一种氮化硅氮化钛结合碳化硅耐火材料及其制备方法。本实施例所述制备方法除下述外其余同实施例7:
所述结合剂为羟丙基甲基纤维素;
所述含氮气氛为氮气气氛。
实施例12
一种氮化硅氮化钛结合碳化硅耐火材料及其制备方法。本实施例所述制备方法除下述外其余同实施例7:
所述结合剂为和羧甲基纤维素;
所述含氮气氛为氮气与氢气的混合气氛。
实施例13
一种氮化硅氮化钛结合碳化硅耐火材料及其制备方法。本实施例所述制备方法是:
先以67~75wt%的碳化硅颗粒、5~13wt%的碳化硅细粉、7~20wt%的硅粉,4.5~10wt%的钛硅铁合金粉、1~2wt%的石墨和1~2wt%的碳黑为原料,外加所述原料5~8wt%的结合剂,再于混碾机中混练,困料,成型,干燥;然后在含氮气氛中进行热处理,制得氮化硅氮化钛结合碳化硅耐火材料。
所述热处理的升温制度是:先升温至800~1000℃,保温5~12h;再升温至1020~1300℃,保温0.5~7h;然后升温至1320~1450℃,保温7~12h。
所述结合剂为沥青。
所述含氮气氛为埋碳气氛。
实施例14
一种氮化硅氮化钛结合碳化硅耐火材料及其制备方法。本实施例所述制备方法除下述外其余同实施例13:
所述结合剂为酚醛树脂;
所述含氮气氛为氨气气氛。
实施例15
一种氮化硅氮化钛结合碳化硅耐火材料及其制备方法。本实施例所述制备方法除下述外其余同实施例13:
所述结合剂为聚乙烯醇;
所述含氮气氛为氮气气氛。
实施例16
一种氮化硅氮化钛结合碳化硅耐火材料及其制备方法。本实施例所述制备方法除下述外其余同实施例13:
所述结合剂为淀粉;
所述含氮气氛为氮气与氢气的混合气氛。
实施例17
一种氮化硅氮化钛结合碳化硅耐火材料及其制备方法。本实施例所述制备方法除下述外其余同实施例13:
所述结合剂为羟丙基甲基纤维素;
所述含氮气氛为埋碳气氛。
实施例18
一种氮化硅氮化钛结合碳化硅耐火材料及其制备方法。本实施例所述制备方法除下述外其余同实施例13:
所述结合剂为和羧甲基纤维素;
所述含氮气氛为氨气气氛。
本具体实施方式与现有技术相比具有如下积极效果:
本发明在原料中引入钛硅铁合金和碳材料,在氮化反应过程中,钛硅铁合金除形成Si3N4外,还能形成TiN和SiC等,TiN晶粒呈弥散分布,能起到弥散强化的作用。同时,钛硅铁合金中的Ti5Si3、TiSi2和TiFeSi2等合金相在氮化后的体积膨胀分别为44.7%、65.2%和56.7%,较Si粉氮化过程的体积膨胀(23.5%)更大,能进一步促进制品的致密化,从而进一步提高制品的力学性能,改善制品的抗氧化和抗渣性能。钛硅铁合金的引入还能促进SiC和Si3N4晶须的形成及生长,有助于形成晶须结合,从而提高制品的力学性能。此外,TiN导热性能较好,也有助于提高制品的抗热震性能。
图1为实施例2制备的一种氮化硅氮化钛结合碳化硅耐火材料的XRD图谱;图2为图1所示氮化硅氮化钛结合碳化硅耐火材料的显微结构图;图3为实施例15制备的另一种氮化硅氮化钛结合碳化硅耐火材料的显微结构图。从图1可以看出,除观察到SiC(6H-SiC、4H-SiC)的特征衍射峰外,同时还能观察到有氮化产物α-Si3N4、β-Si3N4、TiN、Si2N2O的特征衍射峰。从图2可以观察到絮状SiC、Si3N4晶须的生成,晶须可提高制品的力学性能,即引入钛硅铁合金和碳材料,促进了制品的致密化,还可以促进SiC、Si3N4晶须的形成及生长,有助于形成晶须结合,从而提高制品的力学性能。从图3可以观察到,在SiC骨料之间形成了反应烧结,生成较为致密的显微结构。
实施例15制备的氮化硅氮化钛结合碳化硅耐火材料经检测:显气孔率为12.0%;耐压强度达到193MPa。相比于氮化硅结合碳化硅耐火材料的显气孔率下降约20%;耐压强度也提高约90%。
本发明以提取自含钛高炉渣的钛硅铁合金为原料,制备氮化硅氮化钛结合碳化硅耐火材料,对钛硅铁合金的高附加值利用具有重要意义,也可以进一步拓宽含钛高炉渣的高附加值利用途径。
因此,本发明生产成本低,制得的氮化硅氮化钛结合碳化硅耐火材料具有结构均匀致密、抗氧化性能优良、高温力学性能优异、抗热震性能好和抗渣蚀性强的特点。
Claims (9)
1.一种氮化硅氮化钛结合碳化硅耐火材料的制备方法,其特征在于,先以55~75wt%的碳化硅颗粒、5~30wt%的碳化硅细粉、5~30wt%的硅粉,0.1~20wt%的钛硅铁合金粉、0~2wt%的石墨和0~2wt%的碳黑为原料,外加所述原料3~8wt%的结合剂,再于混碾机中混练,困料,成型,干燥;然后在含氮气氛中进行热处理,制得氮化硅氮化钛结合碳化硅耐火材料;
所述石墨的质量百分含量和所述碳黑的质量百分含量不同时为0;
所述钛硅铁合金的制备方法是:先向含钛高炉渣中加入占所述含钛高炉渣0~50wt%的碳、0~40wt%的铝、0~40wt%的铁和0~20wt%的镁;混合均匀后进行熔融还原,制得钛硅铁合金;所述碳、铝和镁的质量百分含量不同时为0;
所述热处理的升温制度是:先升温至800~1000℃,保温0~12h;再升温至1020~1300℃,保温0.5~12h;然后升温至1320~1450℃,保温0.5~12h。
2.根据权利要求1所述的氮化硅氮化钛结合碳化硅耐火材料的制备方法,特征在于所述碳化硅颗粒的SiC含量≥96wt%;所述碳化硅颗粒的粒度为0.088~5mm。
3.根据权利要求1所述的氮化硅氮化钛结合碳化硅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≥96wt%;所述碳化硅细粉的粒度≤0.088mm。
4.根据权利要求1所述的氮化硅氮化钛结合碳化硅耐火材料的制备方法,其特征在于所述硅粉的Si含量≥95wt%,粒度≤0.088mm。
5.根据权利要求1所述的氮化硅氮化钛结合碳化硅耐火材料的制备方法,其特征在于所述钛硅铁合金粉的粒度≤0.088mm。
6.根据权利要求1所述的氮化硅氮化钛结合碳化硅耐火材料的制备方法,其特征在于所述结合剂为沥青、酚醛树脂、聚乙烯醇、淀粉、羟丙基甲基纤维素和羧甲基纤维素中的一种。
7.根据权利要求1所述的氮化硅氮化钛结合碳化硅耐火材料的制备方法,其特征在于所述含氮气氛为埋碳气氛、或为氨气气氛、或为氮气气氛、或为氮气与氢气的混合气氛。
8.根据权利要求1所述的氮化硅氮化钛结合碳化硅耐火材料的制备方法,其特征在于所述的含钛高炉渣为以钒钛磁铁矿为主要原料经高炉冶炼产生的冷态或热态含钛高炉渣;含钛高炉渣的TiO2含量为12~30wt%。
9.一种氮化硅氮化钛结合碳化硅耐火材料,其特征在于所述氮化硅氮化钛结合碳化硅耐火材料是根据权利要求1~8项中任一项所述氮化硅氮化钛结合碳化硅耐火材料的制备方法所制备的氮化硅氮化钛结合碳化硅耐火材料。
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