CN111217597B - 一种特种钢连铸用碱性滑板及其制备工艺 - Google Patents

一种特种钢连铸用碱性滑板及其制备工艺 Download PDF

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CN111217597B
CN111217597B CN201911218556.7A CN201911218556A CN111217597B CN 111217597 B CN111217597 B CN 111217597B CN 201911218556 A CN201911218556 A CN 201911218556A CN 111217597 B CN111217597 B CN 111217597B
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陈松林
蒋正跃
王俊涛
胡小成
刘士范
闫昕
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Ruitai Technology Co ltd
YIXING REFRACTORY MATERIAL CO Ltd
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Abstract

本发明涉及一种特种钢连铸用碱性滑板及其制备工艺,复合各种碳源的优点,通过在镁铝尖晶石为主要原料的滑板中添加金属镁粉,采用CO2作为烧成气氛,在高温下CO2和Mg粉反应,生成MgO和石墨烯。生成的MgO具有高反应活性,和Al2O3原位反应形成尖晶石促进烧结,且原位生成的石墨烯和尖晶石填充细小的孔洞,使得材料更加致密,增强滑板的抗侵蚀性、抗氧化性。

Description

一种特种钢连铸用碱性滑板及其制备工艺
技术领域
本发明涉及一种特种钢连铸用碱性滑板及其制备工艺,属于无机非金属材料学科高温陶瓷和耐火材料领域。
背景技术
世界上约有特种钢近2000个牌号、约50000个品种规格。我国随着工业化深入和装备制造挺进高新领域,风电、核电、高铁、大飞机、石化、汽车等新兴产业所需而普钢无法替代的高品质、高性能、个性化特钢产品市场将急剧增长。在特种钢的冶炼中,为了消除铝脱氧产物造成的水口堵塞,需要对钢水进行钙处理,但是钢水中和渣中浓度增加,它们会与滑板中的成分发生反应生成低熔点物质,从而造成滑板损毁。我国100 t以上的大型钢包滑板普遍使用烧成铝锆碳滑板,使用寿命2~4次。中小型钢包用滑板考虑到成本,材质主要为铝碳质,工艺分烧成、轻烧(中温处理)和不烧3种,寿命通常为1~ 3次,而铝碳质滑板在特种钢浇铸中使用寿命仅为1次。碳结合的铝碳质及铝锆碳质滑板两种滑板抗Ca侵蚀能力差,难以适应钙处理钢、高氧钢、优质钢、沸腾钢、镇静钢、半镇静钢等特种钢连铸的要求。本发明专为钙处理钢、高氧钢、洁净钢冶炼提供性能优越、成本较低、使用安全稳定的镁铝尖晶石碳质滑板,满足特种钢苛刻的使用条件及安全使用要求。
发明内容
一种特种钢连铸用碱性滑板的原料配方(重量百分含量)如下:
(1)粒度3~1mm的镁铝尖晶石,25~50%;
(2)粒度1~0mm的镁铝尖晶石,22~33%;
(3)粒度≤0.045mm的镁铝尖晶石,13~18%;
(4)粒度0.002~0.005mm的富铝尖晶石(A90),7~11%;
(5)鳞片石墨,1~2%;
(6)炭黑,1~2%;
(7)粒度≤0.045mm的金属镁粉,3~6%;
(8)粒度≤0.045mm的金属镁铝合金粉,1~3%;
(9)粒度≤0.045mm碳化硼,1%;
(10)另外加复合树脂,+4~6%;
(11)二氧化碳气体。
原料(10)复合树脂另外加入,不计入原料总质量百分比内。复合树脂由3~1比例的有机硅树脂和酚醛树脂混合制得。原料(11)二氧化碳气体用在烧成时的气氛炉内,不计入原料总质量百分比内。反应炉内保持0.2~0.3MPa的CO2气体压力。原料里面没有价格昂贵的石墨烯材料,石墨烯材料是在滑板烧成时金属镁粉和CO2反应获得。
具体工艺过程包括以下几部分:
(1)按比例称量粒度≤0.045mm的镁铝尖晶石、粒度≤0.045mm的金属镁粉、粒度≤0.045mm的金属镁铝合金粉、粒度≤0.045mm碳化硼粉、粒度0.002~0.005mm的富铝尖晶石(A90),进行强力预混,预混时间在15~20min。
(2)将有机硅树脂和酚醛树脂按重量3~1的比例预先混合,制得复合树脂。
(3)按比例称量粒度3~1mm的镁铝尖晶石、粒度1~0mm的镁铝尖晶石、鳞片石墨、炭黑,进行干混3~5min,然后加入复合树脂,混合2~3min,再加入预混细粉料,强力混碾15~30min。
(4)强力混碾后,用5mm的筛子筛分,去除团聚大块。
(5)密闭困料24~36h。
(6)压制成型。
(7)自然干燥24~48h后,再在200~280℃干燥24~48h。
(8)装入气氛炉内烧成,通0.2~0.3MPa压力的CO2气体,在1450~1550℃保温5~8h。
(9)烧成后自然冷却后磨削,打箍。
本发明的滑板与特种钢水接触造成损伤扩大的机理是脱碳导致组织脆化,钢中成分和钢中夹杂物与耐火材料组织反应生成低熔点物质等。镁铝碳质碱性滑板材质能克服了铝碳滑板材料易和特种钢水反应形成低熔点的缺点,开发适用于特种钢的碱性成为迫切需求。碱性镁碳材质(MgO-C)的滑板由于碳的存在而具有优异的抗侵蚀性能,但缺点易被氧化和对特种钢增碳污染也是由碳引起。碳素是碳复合耐火材料的重要组分,碳具有多种同素异构,耐火材料中多用的碳素材料一般是石墨和无定形碳。天然石墨的化学成分主要是C,同时还含少量的杂质。鳞片状石墨具有明显的定向晶体结构鳞片状石墨的熔点高达 3700℃,它对各种金属和熔渣的浸润性低,具有较好的耐侵蚀性。由于石墨结晶层之间结合力比较弱,将鳞片状石墨加入到滑板材料中可改善滑板的滑动性。焦碳和碳黑都属于无定形碳。无定形碳与石墨的性能相比,导热系数小得多,缺点在于气孔率高,气孔大。必须经过浸渍焦油填隙处理才能使气孔率降低,强度提高。碳黑具有极高的细度和活性,在铝碳或铝碳锆滑板中引入碳黑,可与滑板中的金属添加剂(铝、硅等)反应,生成碳化物,赋予滑板极高的常温和高温强度,提高滑板的耐磨性。
本发明使用鳞片石墨、炭黑等多种碳源方式,复合各种碳源的优点,同时引入已知的最薄、最坚硬的石墨烯纳米碳源提高滑板的低温强度,制备高性能低碳尖晶石碳碱性滑板。引入的石墨烯作为纳米尺度细小且均匀分散的碳源可以减少滑板碳含量,降低特种钢受碳污染的风险。引入的石墨烯复合粉体产生大量的微小的塑性组元,且在烧成过程中石墨烯和纳米硅反应生成大量碳化硅晶须,提高了材料的强度、韧性、抗侵蚀性和抗热震性。引入的方法是通过在镁铝尖晶石为主要原料的滑板中添加金属镁粉,采用CO2作为烧成气氛。在高温下CO2和Mg粉反应,生成MgO和石墨烯。同时,新生成MgO具有高反应活性,和Al2O3原位反应形成尖晶石促进烧结,且原位生成的石墨烯和尖晶石填充细小的孔洞,使得材料更加致密,增强滑板的抗侵蚀性、抗氧化性。
本发明的特种钢连铸用碱性滑板制备工艺的技术特点有3个方面:(1)采用多种碳源方式引入到滑板体系,使得滑板的碳含量降低,较少或不污染特种钢水的化学成分。其中引入二维的碳纳米材料石墨烯,解决了在碱性滑板碳含量降低至1~3%时,滑板的抗侵蚀性不降低,而抗氧化性提高,抗热震性能提高。(2)引入石墨烯的方法是在尖晶石滑板中加入金属Mg粉,在CO2气氛中烧结。镁粉既是抗氧化剂,也是原位反应的原材料,通过镁粉和二氧化碳反应得到MgO和石墨烯。(3)新生成的MgO和石墨烯具有良好的反应活性,MgO和Al2O3原位反应形成尖晶石,而石墨烯和纳米硅添加剂反应形成SiC晶须,达到致密烧结,保证了特种钢连铸用滑板的强度、抗氧化性和抗侵蚀性。
实施例一
原料规格和配方(重量百分含量)如下:
(1)粒度3~1mm的镁铝尖晶石,25%;
(2)粒度1~0mm的镁铝尖晶石,33%;
(3)粒度≤0.045mm的镁铝尖晶石,18%;
(4)粒度0.002~0.005mm的富铝尖晶石(A90),11%;
(5)鳞片石墨,1%;
(6)炭黑,2%;
(7)粒度≤0.045mm的金属镁粉,6%;
(8)粒度≤0.045mm的金属镁铝合金粉,3%;
(9)粒度≤0.045mm碳化硼,1%;
(10)另外加复合树脂,+6%;
(11)二氧化碳气体。
原料(10)复合树脂另外加入,不计入原料总质量百分比内。复合树脂由3:1比例的有机硅树脂和酚醛树脂混合制得。原料(11)二氧化碳气体用在烧成时的气氛炉内,不计入原料总质量百分比内。反应炉内保持0.2MPa的CO2气体压力。原料里面没有价格昂贵的石墨烯材料,石墨烯材料是在滑板烧成时金属镁粉和CO2反应获得。
本发明的具体工艺过程包括以下几部分:
(1)按比例称量粒度≤0.045mm的镁铝尖晶石、粒度≤0.045mm的金属镁粉、粒度≤0.045mm的金属镁铝合金粉、粒度≤0.045mm碳化硼粉、粒度0.002~0.005mm的富铝尖晶石(A90),进行强力预混,预混时间在20min。
(2)将有机硅树脂和酚醛树脂按重量3:1的比例预先混合,制得复合树脂。
(3)按比例称量粒度3~1mm的镁铝尖晶石、粒度1~0mm的镁铝尖晶石、鳞片石墨、炭黑,进行干混3min,然后加入复合树脂,混合2min,再加入预混细粉料,强力混碾30min。
(4)强力混碾后,用5mm的筛子筛分,去除团聚大块。
(5)密闭困料36h。
(6)压制成型。
(7)自然干燥48h后,再在280℃干燥24h。
(8)装入气氛炉内烧成,通0.2MPa压力的CO2气体,在1450℃保温8h。
(9)烧成后自然冷却后磨削,打箍。
表1列出了实施例一的原料规格和配方及其性能。扫描电镜形貌图也证实了材料里面含有石墨烯,如图1. 滑板的SEM形貌。箭头指的薄片就是石墨烯。
性能测试结果表明含有石墨烯的碱性滑板在低温时碱性滑板耐压强度较高,达137MPa;在1400℃高温耐压强度较高变化很小,仍然134MPa。其抗折强度在常温时30MPa,在1100℃高温抗折强度27 MPa,说明发明的碱性滑板的强度对温度的敏感性很低。其抗热震性能也较好,1100℃×0.5h时抗热震次数达10次。抗氧化性较强,1550℃×3h氧化面积比为12.2%。应用于华某钢厂浇铸温度1620~1650℃,经钙处理钢水,连滑5次,轻微裂纹,大大超过铝碳滑板仅仅连滑2次的使用效果。
实施例二
原料规格和配方(重量百分含量)如下:
(1)粒度3~1mm的镁铝尖晶石,38%;
(2)粒度1~0mm的镁铝尖晶石,28%;
(3)粒度≤0.045mm的镁铝尖晶石,15%;
(4)粒度0.002~0.005mm的富铝尖晶石(A90),9%;
(5)鳞片石墨,1.5%;
(6)炭黑,1.5%;
(7)粒度≤0.045mm的金属镁粉,4%;
(8)粒度≤0.045mm的金属镁铝合金粉,2%;
(9)粒度≤0.045mm碳化硼,1%;
(10)另外加复合树脂,+5%;
(11)二氧化碳气体。
原料(10)复合树脂另外加入,不计入原料总质量百分比内。复合树脂由2:1比例的有机硅树脂和酚醛树脂混合制得。原料(11)二氧化碳气体用在烧成时的气氛炉内,不计入原料总质量百分比内。反应炉内保持0.2MPa的CO2气体压力。原料里面没有价格昂贵的石墨烯材料,石墨烯材料是在滑板烧成时金属镁粉和CO2反应获得。
本发明的具体工艺过程包括以下几部分:
(1)按比例称量粒度≤0.045mm的镁铝尖晶石、粒度≤0.045mm的金属镁粉、粒度≤0.045mm的金属镁铝合金粉、粒度≤0.045mm碳化硼粉、粒度0.002~0.005mm的富铝尖晶石(A90),进行强力预混,预混时间在15min。
(2)将有机硅树脂和酚醛树脂按重量2:1的比例预先混合,制得复合树脂。
(3)按比例称量粒度3~1mm的镁铝尖晶石、粒度1~0mm的镁铝尖晶石、鳞片石墨、炭黑,进行干混4min,然后加入复合树脂,混合2min,再加入预混细粉料,强力混碾20min。
(4)强力混碾后,用5mm的筛子筛分,去除团聚大块。
(5)密闭困料24h。
(6)压制成型。
(7)自然干燥24h后,再在260℃干燥24h。
(8)装入气氛炉内烧成,通0.2MPa压力的CO2气体,在1500℃保温6h。
(9)烧成后自然冷却后磨削,打箍。
表1列出了实施例二的原料规格和配方及其性能。性能测试结果表明含有石墨烯的碱性滑板在低温时碱性滑板耐压强度较高,达144MPa;在1400℃高温耐压强度较高变化很小,仍然140MPa。其抗折强度在常温时32MPa,在1100℃高温抗折强度27 MPa,说明发明的碱性滑板的强度对温度的敏感性很低。其抗热震性能也较好,1100℃×0.5h时抗热震次数达10次。抗氧化性较强,1550℃×3h氧化面积比为11.9%。应用于新某钢厂浇铸温度1630~1650℃,高铝镇定钢水,连滑6次,贯穿裂纹,大大超过铝碳滑板仅仅连滑2次的使用效果。
实施例三
原料规格和配方(重量百分含量)如下:
(1)粒度3~1mm的镁铝尖晶石,50%;
(2)粒度1~0mm的镁铝尖晶石,22%;
(3)粒度≤0.045mm的镁铝尖晶石,13%;
(4)粒度0.002~0.005mm的富铝尖晶石(A90),7%;
(5)鳞片石墨,2%;
(6)炭黑,1%;
(7)粒度≤0.045mm的金属镁粉,3%;
(8)粒度≤0.045mm的金属镁铝合金粉,1%;
(9)粒度≤0.045mm碳化硼,1%;
(10)另外加复合树脂,+4%;
(11)二氧化碳气体。
原料(10)复合树脂另外加入,不计入原料总质量百分比内。复合树脂由2:1比例的有机硅树脂和酚醛树脂混合制得。原料(11)二氧化碳气体用在烧成时的气氛炉内,不计入原料总质量百分比内。反应炉内保持0.2MPa的CO2气体压力。原料里面没有价格昂贵的石墨烯材料,石墨烯材料是在滑板烧成时金属镁粉和CO2反应获得。
本发明的具体工艺过程包括以下几部分:
(1)按比例称量粒度≤0.045mm的镁铝尖晶石、粒度≤0.045mm的金属镁粉、粒度≤0.045mm的金属镁铝合金粉、粒度≤0.045mm碳化硼粉、粒度0.002~0.005mm的富铝尖晶石(A90),进行强力预混,预混时间在15min。
(2)将有机硅树脂和酚醛树脂按重量1:1的比例预先混合,制得复合树脂。
(3)按比例称量粒度3~1mm的镁铝尖晶石、粒度1~0mm的镁铝尖晶石、鳞片石墨、炭黑,进行干混5min,然后加入复合树脂,混合3min,再加入预混细粉料,强力混碾15min。
(4)强力混碾后,用5mm的筛子筛分,去除团聚大块。
(5)密闭困料24h。
(6)压制成型。
(7)自然干燥24h后,再在200℃干燥48h。
(8)装入气氛炉内烧成,通0.3MPa压力的CO2气体,在1550℃保温5h。
(9)烧成后自然冷却后磨削,打箍。
表1列出了实施例三的原料规格和配方及其性能。性能测试结果表明含有石墨烯的碱性滑板在低温时碱性滑板耐压强度较高,达156MPa;在1400℃高温耐压强度较高变化很小,仍然148MPa。其抗折强度在常温时33MPa,在1100℃高温抗折强度28MPa,说明发明的碱性滑板的强度对温度的敏感性很低。其抗热震性能也较好,1100℃×0.5h时抗热震次数达10次。抗氧化性较强,1550℃×3h氧化面积比13.6%。应用于某武钢厂300吨氧气顶吹钢包,浇铸硅钢品种钢,连滑5次,有拉毛现象,大大超过铝碳滑板仅仅连滑2次的使用效果。
表1特种钢浇铸用碱性滑板的实施实例的原料规格、配方及其性能对照表

Claims (2)

1.一种特种钢连铸用碱性滑板,原料以重量百分含量计为:
(1)粒度3~1mm的镁铝尖晶石,25~50%;
(2)粒度1~0mm的镁铝尖晶石,22~33%;
(3)粒度≤0.045mm的镁铝尖晶石,13~18%;
(4)粒度0.002~0.005mm的富铝尖晶石A90,7~11%;
(5)鳞片石墨,1~2%;
(6)炭黑,1~2%;
(7)粒度≤0.045mm的金属镁粉,3~6%;
(8)粒度≤0.045mm的金属镁铝合金粉,1~3%;
(9)粒度≤0.045mm碳化硼,1%;
(10)另外加复合树脂,4~6%;
(11)二氧化碳气体;
原料(10)复合树脂另外加入,不计入原料总质量百分比内;复合树脂由3~1比例的有机硅树脂和酚醛树脂混合制得;原料(11)二氧化碳气体用在烧成时的气氛炉内,不计入原料总质量百分比内。
2.权利要求1所述的特种钢连铸用碱性滑板的制备工艺,包括如下步骤:
(1)按比例称量粒度≤0.045mm的镁铝尖晶石、粒度≤0.045mm的金属镁粉、粒度≤0.045mm的金属镁铝合金粉、粒度≤0.045mm碳化硼粉、粒度0.002~0.005mm的富铝尖晶石A90,进行强力预混,预混时间在15~20min;
(2)将有机硅树脂和酚醛树脂按重量3~1的比例预先混合,制得复合树脂;
(3)按比例称量粒度3~1mm的镁铝尖晶石、粒度1~0mm的镁铝尖晶石、鳞片石墨、炭黑,进行干混3~5min,然后加入复合树脂,混合2~3min,再加入预混细粉料,强力混碾15~30min;
(4)强力混碾后,用5mm的筛子筛分,去除团聚大块;
(5)密闭困料24~36h;
(6)压制成型;
(7)自然干燥24~48h后,再在200~280℃干燥24~48h;
(8)装入气氛炉内烧成,通0.2~0.3MPa压力的CO2气体,在1450~1550℃保温5~8h;
(9)烧成后自然冷却后磨削,打箍。
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CN108751948A (zh) * 2018-06-20 2018-11-06 马鞍山利尔开元新材料有限公司 一种含改性石墨中温预处理低碳镁质滑板砖及其制备方法
CN109052373A (zh) * 2018-07-27 2018-12-21 同创科鑫材料科技有限公司 一种基于燃烧合成反应制备石墨烯复合材料的方法

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