CN112341201A - 一种自结合碳化硅耐火材料及其制备方法 - Google Patents

一种自结合碳化硅耐火材料及其制备方法 Download PDF

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CN112341201A
CN112341201A CN202011247771.2A CN202011247771A CN112341201A CN 112341201 A CN112341201 A CN 112341201A CN 202011247771 A CN202011247771 A CN 202011247771A CN 112341201 A CN112341201 A CN 112341201A
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silicon carbide
powder
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董良军
李亚伟
桑绍柏
程伦
陆国峰
程茜
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Yixing Dingshan Refractory Material Co ltd
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Abstract

本发明涉及一种自结合碳化硅耐火材料，由经无水乙醇稀释后的改性树脂和碳化硅原料制备得到，所述改性树脂由热固性酚醛树脂、无水乙醇和碳化硼制备得到，所述碳化硅原料由至少五种不同粒径的碳化硅颗粒、金属硅粉、石墨粉、硅灰和热固性树脂粉制备得到。本发明制备方法在烧制达到560℃时，碳化硼会与氧气发生反应生成液相的氧化硼和二氧化碳，且会先于金属硅氧化，其玻璃相容易熔出从而封闭气孔或溢出表面形成一层致密的氧化膜，而且生成的二氧化碳会从气孔中逸出，对于玻璃相的熔出起到一定的引导和促进作用，这样就可以隔绝空气，使自结合碳化硅制品内部形成还原性气氛，使金属硅粉与石墨能够反应生成碳化硅晶须，以此达到烧结的目的。

Description

一种自结合碳化硅耐火材料及其制备方法
技术领域
本发明属于耐火材料技术领域，尤其涉及一种自结合碳化硅耐火材料及其制备方法。
背景技术
SiC材料因具有高温强度大，抗氧化性好，，耐磨损，热稳定性好，热膨胀系数小，热导率大，硬度高等优良特性而被广泛应用于各种领域。SiC是一种共价键很强的材料，烧结时的扩散速率相当低，同时其颗粒表面往往覆盖一层相当薄的氧化层，起扩散势垒的作用。没有烧结添加剂，纯碳化硅是很难烧结的。
现今常见的碳化硅含量高且高强度碳化硅制品主要分为Si3N4结合SiC、Sialon结合SiC、Si2N2O结合SiC以及SiC自结合SiC。前三者必须在氮气气氛下烧成，SiC自结合SiC要在惰性气体气氛下或者用焦炭石墨等进行埋炭烧成，这样烧制的碳化硅产品对设备要求很高，同时产量较低，成本也非常高。
发明内容
发明目的：本发明的目的在于解决现有的高端碳化硅制品由于需要在特殊的气体气氛下烧成，所以对烧成设备要求高，产量低、成本高的问题。
技术方案：为实现上述目的，本发明提供以下技术方案：
一种自结合碳化硅耐火材料，由经无水乙醇稀释后的改性树脂和碳化硅原料制备得到，所述改性树脂由热固性酚醛树脂、无水乙醇和碳化硼制备得到，所述碳化硅原料由至少五种不同粒径的碳化硅颗粒、金属硅粉、石墨粉、硅灰和热固性树脂粉制备得到。
进一步地，所述改性树脂为热固性酚醛树脂、无水乙醇和碳化硼按照重量配比3.5:2:1混合搅拌后得到的混合物。
先用无水乙醇将树脂稀释，便于我们将碳化硼均匀混合到结合剂酚醛树脂中又不会使其粘度过大，这样做有两个好处：
一是可以将碳化硼更加均匀的包裹在颗粒表面；
二是经碳化硼改性过的树脂具有更好的常温强度。
进一步地，所述碳化硅原料按重量份数包括42～48份粒径为1～3mm的碳化硅，22～26份粒径为0～1mm的碳化硅，5～9份粒径为200目的碳化硅，8～12份粒径为800目的碳化硅,3～9份粒径为1500目的碳化硅，3～7份金属硅粉，1份石墨粉,1份硅灰，1份热固性树脂粉。
进一步地，所述碳化硼为粉粒状，粒径大小为2000目。
进一步地，所述石墨粉要求粒径325目以下，且碳含量大于97％，金属硅粉粒径为325目。
一种自结合碳化硅耐火材料的制备方法，包括以下步骤：
1)分别按照改性树脂和碳化硅原料的配比要求进行原料称取；
2)将按照配比混合完成的热固性酚醛树脂、无水乙醇和碳化硼放在高速搅拌器中搅拌均匀，形成改性树脂；
3)将粉料放在球磨桶内球磨均匀与事先制作好的改性树脂作为备用；
4)将碳化硅原料中粒径为1～3mm的碳化硅和粒径为0～1mm的碳化硅所混合完成的颗粒混合物放入混碾机中混合3分钟，然后边搅拌边加入事先制作好的改性树脂，继续持续搅拌3分钟；
5)搅拌暂停，加入碳化硅原料预混好除步骤4)中的其他粉料继续混碾10分钟；
6)困料24小时后压机成型；
7)在90～110℃烘干，在1400℃～1450℃下烧成。
进一步地，所述步骤7)中，在烧制过程中，先将温度提升至560℃，并保温6h。
在烧制过程中，我们先将温度提升至560℃，然后保温6h，在这个温度下，碳化硼粒径小，活性高，会较快与氧气发生反应生成液相的氧化硼和二氧化碳，且会先于325目金属硅氧化(金属硅粒径太小会导致活性太高先氧化，粒径太大不利于与石墨反应生成碳化硅晶须)，由于碳化硅制品属于非浸润型，其玻璃相容易熔出从而封闭气孔或溢出表面形成一层致密的氧化膜，而且生成的二氧化碳会从气孔中逸出，对于玻璃相的熔出起到一定的引导和促进作用，这样就可以隔绝空气，使自结合碳化硅制品内部形成还原性气氛，使金属硅粉与石墨能够反应生成碳化硅晶须，以此达到烧结的目的。这样我们就无需通入惰性保护气体或者埋炭烧成了，极大地简化了生产过程降低了成本。
有益效果：本发明与现有技术相比具有如下积极效果：
采用本发明的技术方案，高端碳化硅制品无需通入惰性保护气体或者埋炭烧成，极大地简化了生产过程，降低了成本。
附图说明
图1为本发明制备得到的碳化硅制品切割后的显微镜下断面基质部分10000倍放大结构示意图；
图2为本发明制备得到的碳化硅制品切割后的显微镜下断面2000倍放大结构示意图。
具体实施方式
下面结合具体实施方式对本发明作进一步的描述，并非对其保护范围的限制。
实施例1
一种自结合碳化硅耐火材料，由经无水乙醇稀释后的改性树脂和碳化硅原料制备得到，所述改性树脂由热固性酚醛树脂、无水乙醇和碳化硼制备得到，所述碳化硅原料由至少五种不同粒径的碳化硅颗粒、金属硅粉、石墨粉、硅灰和热固性树脂粉制备得到。
改性树脂为热固性酚醛树脂、无水乙醇和碳化硼按照重量配比3.5:2:1混合搅拌后得到的混合物。
先用无水乙醇将树脂稀释，便于我们将碳化硼均匀混合到结合剂酚醛树脂中又不会使其粘度过大，这样做有两个好处：
一是可以将碳化硼更加均匀的包裹在颗粒表面；
二是经碳化硼改性过的树脂具有更好的常温强度。
碳化硅原料按重量份数包括48份粒径为3mm的碳化硅，26份粒径为1mm的碳化硅，9份粒径为200目的碳化硅，12份粒径为800目的碳化硅,9份粒径为1500目的碳化硅，7份金属硅粉，1份石墨粉,1份硅灰，1份热固性树脂粉。
碳化硼为粉粒状，粒径大小为2000目。
石墨粉要求粒径325目以下，且碳含量大于97％，金属硅粉粒径为325目。
实施例2
一种自结合碳化硅耐火材料，由经无水乙醇稀释后的改性树脂和碳化硅原料制备得到，所述改性树脂由热固性酚醛树脂、无水乙醇和碳化硼制备得到，所述碳化硅原料由至少五种不同粒径的碳化硅颗粒、金属硅粉、石墨粉、硅灰和热固性树脂粉制备得到。
改性树脂为热固性酚醛树脂、无水乙醇和碳化硼按照重量配比3.5:2:1混合搅拌后得到的混合物。
先用无水乙醇将树脂稀释，便于我们将碳化硼均匀混合到结合剂酚醛树脂中又不会使其粘度过大，这样做有两个好处：
一是可以将碳化硼更加均匀的包裹在颗粒表面；
二是经碳化硼改性过的树脂具有更好的常温强度。
碳化硅原料按重量份数包括42份粒径为1mm的碳化硅，22份粒径为0.01mm的碳化硅，5份粒径为200目的碳化硅，8份粒径为800目的碳化硅,3份粒径为1500目的碳化硅，3份金属硅粉，1份石墨粉,1份硅灰，1份热固性树脂粉。
碳化硼为粉粒状，粒径大小为2000目。
石墨粉要求粒径325目以下，且碳含量大于97％，金属硅粉粒径为325目。
实施例3
一种自结合碳化硅耐火材料的制备方法，包括以下步骤：
1)分别按照改性树脂和碳化硅原料的配比要求进行原料称取；
2)将按照配比混合完成的热固性酚醛树脂、无水乙醇和碳化硼放在高速搅拌器中搅拌均匀，形成改性树脂；
3)将粉料放在球磨桶内球磨均匀与事先制作好的改性树脂作为备用；
4)将碳化硅原料中粒径为1～3mm的碳化硅和粒径为0～1mm的碳化硅所混合完成的颗粒混合物放入混碾机中混合3分钟，然后边搅拌边加入事先制作好的改性树脂，继续持续搅拌3分钟；
5)搅拌暂停，加入碳化硅原料预混好除步骤4)中的其他粉料继续混碾10分钟；
6)困料24小时后压机成型；
7)在90～110℃烘干，在1400℃～1450℃下烧成。
在烧制过程中，先将温度提升至560℃，并保温6h。
在烧制过程中，我们先将温度提升至560℃，然后保温6h，在这个温度下，碳化硼粒径小，活性高，会较快与氧气发生反应生成液相的氧化硼和二氧化碳，且会先于325目金属硅氧化(金属硅粒径太小会导致活性太高先氧化，粒径太大不利于与石墨反应生成碳化硅晶须)，由于碳化硅制品属于非浸润型，其玻璃相容易熔出从而封闭气孔或溢出表面形成一层致密的氧化膜，而且生成的二氧化碳会从气孔中逸出，对于玻璃相的熔出起到一定的引导和促进作用，这样就可以隔绝空气，使自结合碳化硅制品内部形成还原性气氛，使金属硅粉与石墨能够反应生成碳化硅晶须，以此达到烧结的目的。这样我们就无需通入惰性保护气体或者埋炭烧成了，极大地简化了生产过程降低了成本。
采用本实施例制备方法制备得到产品指标如下：
项目 指标
常温抗折强度Mpa ≥40
常温耐压强度Mpa ≥180
体积密度g/cm<sup>3</sup> ≥2.76
显气孔率％ ≤9.5
热震次数(1100℃水冷)次 ≥30
采用本实施例制备方法制备得到的碳化硅制品切割后的断面2000倍放大显微结构示意图如图2所示，可以看见，基质(颗粒之间填充的粉料)对碳化硅骨料连接紧密而形成了致密的结构。
对应的，如图1所示，对基质部分进行局部放大10000倍，大量的碳化硅晶须存在且具有一定的网络结构。

Claims (7)

1.一种自结合碳化硅耐火材料，其特征在于：由经无水乙醇稀释后的改性树脂和碳化硅原料制备得到，所述改性树脂由热固性酚醛树脂、无水乙醇和碳化硼制备得到，所述碳化硅原料由至少五种不同粒径的碳化硅颗粒、金属硅粉、石墨粉、硅灰和热固性树脂粉制备得到。
2.根据权利要求1所述的自结合碳化硅耐火材料，其特征在于：所述改性树脂为热固性酚醛树脂、无水乙醇和碳化硼按照重量配比3.5:2:1混合搅拌后得到的混合物。
3.根据权利要求1所述的自结合碳化硅耐火材料，其特征在于：所述碳化硅原料按重量份数包括42～48份粒径为1～3mm的碳化硅，22～26份粒径为0～1mm的碳化硅，5～9份粒径为200目的碳化硅，8～12份粒径为800目的碳化硅,3～9份粒径为1500目的碳化硅，3～7份金属硅粉，1份石墨粉,1份硅灰，1份热固性树脂粉。
4.根据权利要求2所述的自结合碳化硅耐火材料，其特征在于：所述碳化硼为粉粒状，粒径大小为2000目。
5.根据权利要求3所述的自结合碳化硅耐火材料，其特征在于：所述石墨粉要求粒径325目以下，且碳含量大于97％，金属硅粉粒径为325目。
6.一种如权利要求1所述的自结合碳化硅耐火材料的制备方法，其特征在于：包括以下步骤：
1)分别按照改性树脂和碳化硅原料的配比要求进行原料称取；
2)将按照配比混合完成的热固性酚醛树脂、无水乙醇和碳化硼放在高速搅拌器中搅拌均匀，形成改性树脂；
3)将粉料放在球磨桶内球磨均匀与事先制作好的改性树脂作为备用；
4)将碳化硅原料中粒径为1～3mm的碳化硅和粒径为0～1mm的碳化硅所混合完成的颗粒混合物放入混碾机中混合3分钟，然后边搅拌边加入事先制作好的改性树脂，继续持续搅拌3分钟；
5)搅拌暂停，加入碳化硅原料预混好除步骤4)中的其他粉料继续混碾10分钟；
6)困料24小时后压机成型；
7)在90～110℃烘干，在1400℃～1450℃下烧成。
7.根据权利要求6所述的自结合碳化硅耐火材料的制备方法，其特征在于：所述步骤7)中，在烧制过程中，先将温度提升至560℃，并保温6h。
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