CN111348903A - 一种铝碳质整体塞棒及其制备方法 - Google Patents

一种铝碳质整体塞棒及其制备方法 Download PDF

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CN111348903A
CN111348903A CN201910597808.5A CN201910597808A CN111348903A CN 111348903 A CN111348903 A CN 111348903A CN 201910597808 A CN201910597808 A CN 201910597808A CN 111348903 A CN111348903 A CN 111348903A
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马北越
任鑫明
石明东
高陟
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Yingkou Shixing Refractory Technology Co ltd
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Abstract

本发明具体涉及了一种铝碳质整体塞棒及其制备方法。具体制备方案为:按质量分数配料:30%~40%大颗粒电熔刚玉(5~1 mm),20%~30%小颗粒电熔刚玉(1~0.088 mm),10%~20%活性氧化铝,10%~15%碳素,0%~2%抗氧化剂,2%~5%粘结剂,5%~10%硅废料,混炼,成型,热处理。最后在埋碳气氛下,1400~1600℃保温4~6 h制成原位增强的铝碳质整体塞棒材料。原位生成的碳化硅晶须可有效增强塞棒的力学及抗热震性能。本发明的特殊添加是工业废料处理而来,成本低廉,工艺简单。具备放大到工业生产中的可能性。

Description

一种铝碳质整体塞棒及其制备方法
技术领域
本发明属于连铸用耐火材料技术领域,主要涉及了一种铝碳质整体塞棒及其制备方法。
背景技术
铝碳质耐火材料分为不烧和烧成两种。不烧铝碳质耐火材料属于碳结合,主要应用在高炉、铁水预处理等设备。烧成铝碳质耐火材料属于碳结合和陶瓷结合,具有出色的强度、抗渣性和抗热震性,被大量应用于滑动水口及连铸三大件(长水口、浸入式水口、整体塞棒),因此也被称作功能耐火材料。与镁碳材料一样,同属碳复合耐火材料。碳给此类材料提供良好的抗渣侵蚀和抗热震性。
与其他耐火材料不同,因为铝碳材料除了作为结构支撑作用,还发挥着一定的功能特性。如水口主要用来在钢包、中间包和结晶器间传输钢水,塞棒和滑板用来控制钢液流量。因此,与其他结构件耐火材料相比,铝碳材料受到钢水和渣的冲击更为剧烈,损坏率也更高。如何提升铝碳材料的使用性能也一直是耐火材料领域的热点及难点之一。
整体塞棒是控制中间包流入结晶器钢水流速的关键器件,对后续连铸过程起着至关重要的作用。整体塞棒损毁的原因主要是塞棒头部的蚀损造成的,因为塞棒头部最接近出钢口,附近的钢液流速较大,往往是最先被损坏的。目前,可通过添加钢纤维等方式来提高整体塞棒的抗冲刷和蚀损性能,但因为纤维在大颗粒骨料中难以分散,均匀性较差,增强效果并不理想。
发明内容
本发明旨在解决现有技术的缺点,提供一种成本低廉、工艺简单的铝碳质整体塞棒及其制备方法,主要在于其抗剥落性和抗冲刷性能的提升。用该法制备的铝碳塞棒,因为高温原位合成了碳化硅纤维,力学性能、抗热震性,及抗剥落性能都会得到增强。
为了实现上述目的,本发明采用了如下的技术方案:
按质量分数配料:30%~40%大颗粒电熔刚玉(5~1 mm),20%~30%小颗粒电熔刚玉(1~0.088 mm),10%~20%活性氧化铝,10%~15%碳素,0%~2%抗氧化剂,2%~5%粘结剂,5%~10%硅废料,混炼,成型,热处理。最后在埋碳气氛下,1400~1600 ℃保温4~6 h。
所述的电熔刚玉纯度≥98%。活性氧化铝为α-Al2O3,纯度≥99%,粒度小于200目。
所述的碳素为鳞片石墨,纯度≥95%,粒度小于180目。
所述的抗氧化剂为铝粉,纯度≥99%,粒度小于200目。
所述的粘结剂为液态酚醛树脂,工业纯。
所述的硅废料为多晶硅电池生产过程中产生的切割废料,主要为硅,碳化硅,氧化硅,聚乙二醇。为除去杂质,将硅废料先在600 ℃处理5 h。接着用HF酸浸除去杂质和氧化硅。最终得到化学组成为70%~75% Si,20%~30% SiC,0~3% 杂质。
所述的酸浸工艺为,HF酸体积分数10%~20%,时间为3~5 h。
与现有技术相比,本发明的有益效果在于:
(1)本发明除了废料预处理阶段为外加步骤,其余制备过程与传统铝碳材料一致,并不会增加工艺的难度。而且硅废料的预处理过程也比较简单,不会造成成本增加。
(2)硅可以作为抗氧化剂,以减少在配料是抗氧化剂的添加,节省成本。本发明抗氧化剂添加量就明显低于生产实际值。
(3)硅在高温和碳或者一氧化碳反应会原位形成碳化硅晶须。因为碳化硅晶须是原位形成,分散的比外加方式更为均匀,增强效果也要更好。碳化硅晶须除了可以增强铝碳塞棒的强度,防止引钢水冲击引发的热剥落,还能提高其抗热震性。碳化硅也可以提升铝碳塞棒的高温性能,因为碳化硅的高热导率和低热膨胀性。
附图说明
图1为本发明工艺流程图。
具体实施方式
下面结合实施例对本发明作进一步的详细说明。
实施例1
按质量分数配料: 40%大颗粒电熔刚玉(5~1 mm),22%小颗粒电熔刚玉(1~0.088 mm),18%活性氧化铝,10%鳞片石墨,2%铝粉,3%液态酚醛树脂,5%硅废料,混炼,成型,热处理。最后在埋碳气氛下,1400保温6 h。
其中,酸浸HF酸体积分数为15%,处理时间3 h。处理的硅废料具体组成为Si 70%,SiC 28%,其他杂质2%。
本实施相关性能检测结果:
体积密度3.02 g·cm-3,常温耐压强度96.72 MPa,抗热震性(1200 ℃热震1次)保持率为49.77%。用碱度为1.5的精炼渣在1600 ℃保温2 h测试抗渣性,表面几乎无侵蚀和渗透现象。
实施例2
按质量分数配料: 35%大颗粒电熔刚玉(5~1 mm),30%小颗粒电熔刚玉(1~0.088 mm),10%活性氧化铝,13%鳞片石墨,0%铝粉,2%液态酚醛树脂,10%硅废料,混炼,成型,热处理。最后在埋碳气氛下,1600 ℃保温6 h。
其中,酸浸HF酸体积分数为20%,处理时间3 h。处理的硅废料具体组成为Si 75%,SiC 24%,其他杂质1%。
本实施相关性能检测结果:
体积密度3.07 g·cm-3,常温耐压强度91.64 MPa,抗热震性(1200 ℃热震1次)保持率为51.27%。用碱度为1.5的精炼渣在1600 ℃保温2 h测试抗渣性,表面几乎无侵蚀和渗透现象。
实施例3
按质量分数配料:30%大颗粒电熔刚玉(5~1 mm),26%小颗粒电熔刚玉(1~0.088 mm),14%活性氧化铝,13%鳞片石墨,0%铝粉,4%液态酚醛树脂,10%硅废料,混炼,成型,热处理。最后在埋碳气氛下,1600 ℃保温4 h。
其中,酸浸HF酸体积分数为20%,处理时间3 h。处理的硅废料具体组成为Si 73%,SiC 26%,其他杂质1%。
本实施相关性能检测结果:
体积密度2.91 g·cm-3,常温耐压强度87.62 MPa,抗热震性(1200 ℃热震1次)保持率为46.57%。用碱度为1.5的精炼渣在1600 ℃保温2 h测试抗渣性,表面几乎无侵蚀和渗透现象。
实施例4
按质量分数配料:38%大颗粒电熔刚玉(5~1 mm),29%小颗粒电熔刚玉(1~0.088 mm),10%活性氧化铝,12%鳞片石墨,2%铝粉,4%液态酚醛树脂,5%硅废料,混炼,成型,热处理。最后在埋碳气氛下,1500 ℃保温5 h。
其中,酸浸HF酸体积分数为20%,处理时间3 h。处理的硅废料具体组成为Si 73%,SiC 26%,其他杂质1%。
本实施相关性能检测结果:
体积密度2.99 g·cm-3,常温耐压强度93.15 MPa,抗热震性(1200 ℃热震1次)保持率为48.37%。用碱度为1.5的精炼渣在1600 ℃保温2 h测试抗渣性,表面几乎无侵蚀和渗透现象。
实施例5
按质量分数配料: 37%大颗粒电熔刚玉(5~1 mm),26%小颗粒电熔刚玉(1~0.088 mm),15%活性氧化铝,11%鳞片石墨,1%铝粉,3%液态酚醛树脂,7%硅废料,混炼,成型,热处理。最后在埋碳气氛下,1500 ℃保温5 h。
其中,酸浸HF酸体积分数为12%,处理时间4 h。处理的硅废料具体组成为Si 71%,SiC 27%,其他杂质2%。
本实施相关性能检测结果:
体积密度3.11 g·cm-3,常温耐压强度95.84 MPa,抗热震性(1200 ℃热震1次)保持率为52.27%。用碱度为1.5的精炼渣在1600 ℃保温2 h测试抗渣性,表面几乎无侵蚀和渗透现象。

Claims (7)

1.一种铝碳质整体塞棒及其制备方法,其特征在于,按质量分数配料:30%~40%大颗粒电熔刚玉(5~1 mm),20%~30%小颗粒电熔刚玉(1~0.088 mm),10%~20%活性氧化铝,10%~15%碳素,0%~2%抗氧化剂,2%~5%粘结剂,5%~10%硅废料,混炼,成型,热处理,最后在埋碳气氛下,1400~1600 ℃保温4~6 h。
2.根据权利要求1所述的一种铝碳质整体塞棒及其制备方法,其特征在于,所述的电熔刚玉纯度≥98%,活性氧化铝为α-Al2O3,纯度≥99%,粒度小于200目。
3.根据权利要求1所述的一种铝碳质整体塞棒及其制备方法,其特征在于,所述的碳素为鳞片石墨,纯度≥95%,粒度小于180目。
4.根据权利要求1所述的一种铝碳质整体塞棒及其制备方法,其特征在于,所述的抗氧化剂为铝粉,纯度≥99%,粒度小于200目。
5.根据权利要求1所述的一种铝碳质整体塞棒及其制备方法,其特征在于,所述的粘结剂为液态酚醛树脂,工业纯。
6.根据权利要求1所述的一种铝碳质整体塞棒及其制备方法,其特征在于,所述的硅废料为多晶硅电池生产过程中产生的切割废料,主要为硅,碳化硅,氧化硅,聚乙二醇,为除去杂质,将硅废料先在600 ℃处理5 h,接着用HF酸浸除去杂质和氧化硅,最终得到化学组成为70%~75% Si,20%~30% SiC,0~3% 杂质。
7.根据权利要求6所述的一种铝碳质整体塞棒及其制备方法,其特征在于,所述的酸浸工艺为,HF酸体积分数10%~20%,时间为3~5 h。
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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN113999023A (zh) * 2021-09-28 2022-02-01 赛文斯新型材料(无锡)有限公司 用于塞棒的纳米耐火材料制备方法
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CN113999023A (zh) * 2021-09-28 2022-02-01 赛文斯新型材料(无锡)有限公司 用于塞棒的纳米耐火材料制备方法
CN115677330A (zh) * 2022-07-29 2023-02-03 南京钢铁股份有限公司 一种中间包用自润滑盲板及其制备方法
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CN115925397A (zh) * 2022-12-30 2023-04-07 江苏集萃安泰创明先进能源材料研究院有限公司 一种塞棒本体、塞棒及其制备方法
CN115925397B (zh) * 2022-12-30 2024-01-23 江苏集萃安泰创明先进能源材料研究院有限公司 一种塞棒本体、塞棒及其制备方法

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