CN111087229A - 一种纳米材料改性的高抗氧化长水口及其制备工艺 - Google Patents

一种纳米材料改性的高抗氧化长水口及其制备工艺 Download PDF

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CN111087229A
CN111087229A CN201911232108.2A CN201911232108A CN111087229A CN 111087229 A CN111087229 A CN 111087229A CN 201911232108 A CN201911232108 A CN 201911232108A CN 111087229 A CN111087229 A CN 111087229A
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powder
flake graphite
long nozzle
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闫昕
陈松林
魏瀚
王俊涛
胡小成
刘士范
孙旭东
徐琳琳
徐如林
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YIXING REFRACTORY MATERIAL CO Ltd
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Abstract

本发明涉及一种纳米材料改性的高抗氧化长水口及其制备工艺。通过加入纳米级抗氧化剂纳米硅粉，以及采用四氯化硅浸润鳞片石墨，使其对鳞片石墨表面改性；在氮气保护气氛下烧成，可生成填充孔隙、提高材料致密度的氧化物和非氧化物陶瓷增强相，显著提高材料的抗氧化性能，改善材料的力学性能，断裂能和抗热震性。长水口在生产和服役过程中，材料的结合方式主要有树脂结合、碳结合，陶瓷增强结合等多种形式，保持材料强度一致性。

Description

一种纳米材料改性的高抗氧化长水口及其制备工艺
技术领域
本发明涉及一种纳米材料改性的高抗氧化长水口及其制备工艺，属于耐火材料领域。
背景技术
长水口是钢铁连铸生产过程中重要的功能耐火材料，使用时与钢包下水口通过滑板机构连接，将钢水由钢包输送至中间包，起到保护浇注、防止钢水二次氧化的作用。长水口的性能和使用行为直接影响着多炉连浇、连铸效率和铸坯质量。
长水口主要材质有熔融石英和铝碳质。长水口中加入碳质材料，碳很难被炉渣侵蚀，并具有良好的导热性和韧性，从而提高了耐火材料的抗渣性和抗热震性。但是，碳易氧化是含碳材料损毁的重要原因。通常在含碳耐火材料中引入优于碳先氧化的抗氧化剂，提升材料的抗氧化性。
纳米粉具有较好的填充作用，易使材料结构致密化、气孔微细化，可提高抗侵蚀性；在材料中易形成以纳米颗粒为核的类似于“晶内型”的复合结构，可提高材料的抗热震性。此外，纳米粉还具有降低烧结温度、提高反应活性和增强结合的作用等。
本发明研究开发纳米材料改性的高抗氧化长水口，在长水口中添加纳米级抗氧化剂，改善长水口的抗氧化性能，提高材料的力学性能，满足其苛刻的使用要求。
发明内容
本发明的目的在于，研究一种纳米材料改性的高抗氧化长水口及其制备工艺。本发明的原料规格和配方（重量百分含量）如下：
（1）粒度0.50-0.18mm的电熔白刚玉，18~24%；
（2）粒度0.18-0.075mm的电熔白刚玉，8~14%；
（3）粒度≤0.075mm的电熔白刚玉，16~26%；
（4）粒度0.59~0.21mm的电熔锆莫来石，4~6%；
（5）粒度0.21~0 mm的电熔锆莫来石，8~12%；
（6）粒度2μ α氧化铝微粉，5~10%；
（7）895鳞片石墨，18~24%；
（8）纳米硅粉，2~5%；
（9）酚醛树脂粉，+10~12%；（另外加入，不计入原料总质量百分比。）
（10）酒精，+6~7%；（另外加入，不计入原料总质量百分比。）
（11）高纯四氯化硅液体
具体工艺过程包括以下几部分：
（1）按比例称取鳞片石墨倒入四氯化硅中浸泡120分钟，50度烘干24小时备用；
（2）按比例称取粒度2μm的α-Al2O3微粉和纳米硅粉经球磨形成复合粉，球磨时间在90～120分钟；
（3）造粒：按比例称取粒度0.50-0.18mm、粒度0.18-0.075mm、粒度≤0.075mm的电熔白刚玉，粒度0.59~0.21mm、粒度0.21~0 mm的电熔锆莫来石，酚醛树脂粉与工艺（1）烘干的鳞片石墨，工艺（2）制得的混合粉置入造粒机中进行低速搅拌4-5min，中速搅拌4-5min，加入酒精，低速搅拌2-4min，高速搅拌10-15min，得到颗粒料；
（3）筛分：用2mm的筛子筛分，保留筛下料，去除筛上料。
（5）困料：恒温恒湿条件下困料24～36h。
（6）成型：将工艺（5）得到的泥料放入模具中，在100~130MPa等静压条件下压制成型，保压360-480s。
（7）干燥：自然干燥12～24h后，再在200～240℃干燥24～36h。
（8）烧成：在氮化气氛下1350～1450℃烧成，保温6～10小时
（9）烧成后自然冷却后机加工，装铁壳，包装。
本发明通过加入纳米级抗氧化剂纳米硅粉，降低反应温度，生成填充孔隙、提高材料致密度的氧化物和非氧化物陶瓷增强相，显著提高材料的抗氧化性能，改善材料的力学性能；同时采用四氯化硅浸润鳞片石墨，使其对鳞片石墨表面改性，在氮气保护气氛下（1350~1450℃）高温烧成，形成SiC/Si3N4复合陶瓷相，进一步提高材料的抗氧化性，断裂能和抗热震性。长水口在生产和服役过程中，材料的结合方式主要有树脂结合、碳结合，陶瓷增强结合等多种形式，保持了材料强度一致性，并提高材料的热震稳定性。
本发明生产的长水口具有优异抗氧化性、抗侵蚀性及力学性能，在连铸的大型钢包中，使用寿命稳定在12h以上。与现有技术相比，本发明的显著区别特征在于：
（1）性能稳定可靠，抗氧化性能优异。普通铝碳长水口中的碳易氧化，导致材料强度降低，进一步导致材料损毁，本发明中引入添加纳米硅抗氧化剂，其粒径小且分布均匀、比表面积大、表面活性高，其均匀分布在耐火材料基质中；同时在采用四氯化硅对鳞片石墨进行表面改性。纳米硅和改性石墨在高温下与气氛中N2或环境中的C原位反应生成SiC、Si3N4等陶瓷相，不仅填充气孔并提高材料的致密度，而且对材料起到增强增韧的作用，提高材料的抗氧化性、抗侵蚀性及力学性能。
（2）优化细粉加入方式。本发明引入纳米硅粉，考虑到纳米粉末易团聚，分散不均等问题，先将纳米硅粉和α-氧化铝微粉球磨混合，形成复合粉；再将复合粉与其他细粉进行造粒；最终使其均匀填充于耐火材料颗粒间隙内，改善耐火材料的成型性能。
实施例一
原料规格和配方（重量百分含量）如下：
（1）粒度0.50-0.18mm的电熔白刚玉，18%；
（2）粒度0.18-0.075mm的电熔白刚玉，10%；
（3）粒度≤0.075mm的电熔白刚玉，26%；
（4）粒度0.59~0.21mm的电熔锆莫来石，5%；
（5）粒度0.21~0 mm的电熔锆莫来石，8%；
（6）粒度2μ α氧化铝微粉，7%；
（7）895鳞片石墨，24%；
（8）纳米硅粉，2%；
（9）酚醛树脂粉，+12%；（另外加入，不计入原料总质量百分比。）
（10） 酒精，+7%；（另外加入，不计入原料总质量百分比。）
（11） 高纯四氯化硅液体原料
本发明的具体工艺过程包括以下几部分：
（1）按比例称取鳞片石墨24%倒入四氯化硅中浸泡120分钟，50度烘干24小时备用；
（2）按比例称取粒度2μm的α-Al2O3微粉7%和纳米硅粉2%经球磨形成复合粉，球磨时间在90分钟；
（3）造粒：按比例称取粒度0.50-0.18mm、粒度0.18-0.075mm、粒度≤0.075mm的电熔白刚玉分别为18%、10%、26%；粒度0.59~0.21mm、粒度0.21~0 mm的电熔锆莫来石分别为5%、8%；酚醛树脂粉12%；与工艺（1）烘干的鳞片石墨，工艺（2）制得的混合粉置入造粒机中进行低速搅拌4min，中速搅拌5min，加入酒精7%，低速搅拌4min，高速搅拌15min，得到颗粒料；
（3）筛分：用2mm的筛子筛分，保留筛下料，去除筛上料。
（5）困料：恒温恒湿条件下困料36h。
（6）成型：将工艺（5）得到的泥料放入模具中，在130MPa等静压条件下压制成型，保压480s。
（7）干燥：自然干燥12h后，再在220℃干燥30h。
（8）烧成：在氮化气氛下1400℃烧成，保温8小时
（9）烧成后自然冷却后机加工，装铁壳，包装。
表1列出了实施例一的原料规格和配方及其性能。经检测，产品体积密度为2.62g/cm3, 显气孔率为13.1%，常温耐压强度达到33MPa，常温抗折强度10MPa，热震稳定性达到7次，按照国标检测其抗氧化性，其脱碳层仅为4mm；在A钢厂（100吨钢包）试用，平均连续使用13小时，用后长水口完整，扩孔均匀，无掉块、剥落等现象。
实施例二
原料规格和配方（重量百分含量）如下：
（1）粒度0.50-0.18mm的电熔白刚玉，20%；
（2）粒度0.18-0.075mm的电熔白刚玉，14%；
（3）粒度≤0.075mm的电熔白刚玉，16%；
（4）粒度0.59~0.21mm的电熔锆莫来石，4%；
（5）粒度0.21~0 mm的电熔锆莫来石，12%；
（6）粒度2μ α氧化铝微粉，10%；
（7）895鳞片石墨，21%；
（8）纳米硅粉，3%；
（9）酚醛树脂粉，+11%；（另外加入，不计入原料总质量百分比。）
（10） 酒精，+6.5%；（另外加入，不计入原料总质量百分比。）
（11） 高纯四氯化硅液体原料
本发明的具体工艺过程包括以下几部分：
（1）按比例称取鳞片石墨21%倒入四氯化硅中浸泡120分钟，50度烘干24小时备用；
（2）按比例称取粒度2μm的α-Al2O3微粉10%和纳米硅粉3%经球磨形成复合粉，球磨时间在100分钟；
（3）造粒：按比例称取粒度0.50-0.18mm、粒度0.18-0.075mm、粒度≤0.075mm的电熔白刚玉分别为20%、14%、16%；粒度0.59~0.21mm、粒度0.21~0 mm的电熔锆莫来石分别为4%、12%；酚醛树脂粉11%；与工艺（1）烘干的鳞片石墨，工艺（2）制得的混合粉置入造粒机中进行低速搅拌5min，中速搅拌4min，加入酒精6.5%，低速搅拌2min，高速搅拌10min，得到颗粒料；
（3）筛分：用2mm的筛子筛分，保留筛下料，去除筛上料。
（5）困料：恒温恒湿条件下困料24h。
（6）成型：将工艺（5）得到的泥料放入模具中，在100MPa等静压条件下压制成型，保压360s。
（7）干燥：自然干燥24h后，再在200℃干燥36h。
（8）烧成：在氮化气氛下1350℃烧成，保温10小时
（9）烧成后自然冷却后机加工，装铁壳，包装。
表1列出了实施例二的原料规格和配方及其性能。经检测，产品体积密度为2.68g/cm3, 显气孔率为12.4%，常温耐压强度达到36MPa，常温抗折强度9MPa，热震稳定性达到7次，按照国标检测其抗氧化性，其脱碳层仅为3mm；在B钢厂（120吨钢包）试用，平均连续使用12小时以上，正常下线。
实施例三
原料规格和配方（重量百分含量）如下：
（1）粒度0.50-0.18mm的电熔白刚玉，24%；
（2）粒度0.18-0.075mm的电熔白刚玉，8%；
（3）粒度≤0.075mm的电熔白刚玉，24%；
（4）粒度0.59~0.21mm的电熔锆莫来石，6%；
（5）粒度0.21~0 mm的电熔锆莫来石，10%；
（6）粒度2μ α氧化铝微粉，5%；
（7）895鳞片石墨，18%；
（8）纳米硅粉，5%；
（9）酚醛树脂粉，+10%；（另外加入，不计入原料总质量百分比。）
（10） 酒精，+6%；（另外加入，不计入原料总质量百分比。）
（11） 高纯四氯化硅液体原料
本发明的具体工艺过程包括以下几部分：
（1）按比例称取鳞片石墨18%倒入四氯化硅中浸泡120分钟，50度烘干24小时备用；
（2）按比例称取粒度2μm的α-Al2O3微粉5%和纳米硅粉5%经球磨形成复合粉，球磨时间在120分钟；
（3）造粒：按比例称取粒度0.50-0.18mm、粒度0.18-0.075mm、粒度≤0.075mm的电熔白刚玉分别为24%、8%、24%；粒度0.59~0.21mm、粒度0.21~0 mm的电熔锆莫来石分别为6%、10%；酚醛树脂粉10%；与工艺（1）烘干的鳞片石墨，工艺（2）制得的混合粉置入造粒机中进行低速搅拌5min，中速搅拌5min，加入酒精6%，低速搅拌3min，高速搅拌13min，得到颗粒料；
（3）筛分：用2mm的筛子筛分，保留筛下料，去除筛上料。
（5）困料：恒温恒湿条件下困料30h。
（6）成型：将工艺（5）得到的泥料放入模具中，在120MPa等静压条件下压制成型，保压420s。
（7）干燥：自然干燥20h后，再在240℃干燥24h。
（8）在氮化气氛下1450℃烧成，保温6小时
（9）烧成后自然冷却后机加工，装铁壳，包装。
表1列出了实施例三的原料规格和配方及其性能。经检测，产品体积密度为2.68g/cm3, 显气孔率为12.6%，常温耐压强度达到36MPa，常温抗折强度11MPa，热震稳定性达到7次，按照国标检测其抗氧化性，其脱碳层仅为3mm；在C钢厂（300吨钢包）试用，平均连续使用10小时以上，用后长水口完整，无掉块、剥落等现象。
表1 高抗氧化长水口的原料规格、配方及测试性能
Figure DEST_PATH_IMAGE002

Claims (2)

1.一种纳米材料改性的高抗氧化长水口，原料配方按重量百分含量计：
（1）粒度0.50-0.18mm的电熔白刚玉，18~24%；
（2）粒度0.18-0.075mm的电熔白刚玉，8~14%；
（3）粒度≤0.075mm的电熔白刚玉，16~26%；
（4）粒度0.59~0.21mm的电熔锆莫来石，4~6%；
（5）粒度0.21~0 mm的电熔锆莫来石，8~12%；
（6）粒度2μm的 α-氧化铝微粉，5~10%；
（7）895鳞片石墨，18~24%；
（8）纳米硅粉，2~5%；
（9）酚醛树脂粉，+10~12%；另外加入，不计入原料总质量百分比；
（10）酒精，+6~7%；另外加入，不计入原料总质量百分比；
（11）高纯四氯化硅液体。
2.一种权利要求1所述的纳米材料改性的高抗氧化长水口的制备工艺，包括如下步骤：
（1）按比例称取鳞片石墨倒入四氯化硅中浸泡120分钟，50度烘干24小时备用；
（2）按比例称取粒度2μm的α-Al2O3微粉和纳米硅粉经球磨形成复合粉，球磨时间在90～120分钟；
（3）造粒：按比例称取粒度0.50-0.18mm、粒度0.18-0.075mm、粒度≤0.075mm的电熔白刚玉，粒度0.59~0.21mm、粒度0.21~0 mm的电熔锆莫来石，酚醛树脂粉与工艺（1）烘干的鳞片石墨，工艺（2）制得的混合粉置入造粒机中进行低速搅拌4-5min，中速搅拌4-5min，加入酒精，低速搅拌2-4min，高速搅拌10-15min，得到颗粒料；
（4）筛分：用2mm的筛子筛分，保留筛下料，去除筛上料；
（5）困料：恒温恒湿条件下困料24～36h；
（6）成型：将工艺（5）得到的泥料放入模具中，在100~130MPa等静压条件下压制成型，保压360-480s；
（7）干燥：自然干燥12～24h后，再在200～240℃干燥24～36h；
（8）烧成：在氮化气氛下1350～1450℃烧成，保温6～10小时；
（9）烧成后自然冷却后机加工，装铁壳，包装。
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