CN116283299A - 一种增材制造陶瓷微球增强先驱体陶瓷的方法 - Google Patents
一种增材制造陶瓷微球增强先驱体陶瓷的方法 Download PDFInfo
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Abstract
本发明涉及一种增材制造陶瓷微球增强先驱体陶瓷的方法，属于硅基陶瓷成型技术领域。本发明的成型方法，首先将有机硅先驱体乳液法成球后置于管式炉中，氮气或氩气气氛保护，热解得到陶瓷微球；其次，将陶瓷微球、有机硅先驱体、活性稀释剂、光引发剂混合，得到分散均匀的料浆；然后利用增材制造设备打印复杂形状的陶瓷坯体，后处理后制得硅基复合陶瓷。本发明方法简单，成本较低，可明显改善先驱体陶瓷的力学性能。
Description
技术领域
本发明属于硅基陶瓷成型技术领域，更具体地，涉及增材制造陶瓷微球增强先驱体陶瓷的方法。
背景技术
硅基陶瓷具有良好的耐腐蚀性，高温稳定性及优良的力学性能成为结构陶瓷不可或缺的一部分，被广泛应用于航空航天、化工、机械及集成电路等领域。近年来，已经开发出多种成型方法用于制造高密度、高均匀性和高可靠性的硅基陶瓷，如干压成型、冷等静压成型、注浆成型、流延成型、注塑成型等，但是这些传统的成型方法很难制造出结构复杂高精度的陶瓷制品。此外，上述这些加工工艺也非常耗时，成本较高，大大限制了硅基陶瓷材料的进一步发展。因此，有必要开发一种更有效、经济的方法来制备复杂形状的硅基陶瓷。将3D打印技术应用于陶瓷零件制造则为解决上述问题和挑战提供了全新可能。光固化成型技术是一种有效的紫外光固化技术，在制造高精度和高质量的复杂形状陶瓷部件方面具有巨大潜力。相对于Al2O3、SiO2或ZrO2，光固化3D打印深色陶瓷材料(Si3N4, SiC)更具挑战性，这是因为在光固化打印陶瓷浆料时，由于入射光的散射和反射，陶瓷粉末的折射率与光固化树脂的折射率严重不匹配，大大降低了固化深度。有机硅先驱体的3D打印作为一种可热解成陶瓷的替代技术方案受到了广泛的关注，而利用有机先驱体转化法制备的陶瓷收缩较大，陶瓷产率低，力学性能差。因此，需要一种新的方法来解决先驱体陶瓷的力学性能的问题。
发明内容
为了解决上述问题，本发明提供了一种增材制造陶瓷微球增强先驱体陶瓷的方法。
本发明的技术方案为：
本发明的一种增材制造陶瓷微球增强先驱体陶瓷的方法，包括如下具体步骤：
1）将有机硅先驱体乳液法成球后置于管式炉中，氮气或氩气气氛保护，800-1000℃热解得到陶瓷微球；
2）将有机硅先驱体(50wt%-90wt%)、单体(10wt%-50wt%)、光引发剂（1wt%-5wt%）、步骤1）和分散剂（1wt%-5wt%）在磁力搅拌转速400-500r/min下搅拌2-6h，然后加入陶瓷微球（0vol%-60vol%）继续搅拌2-4h，超声分散30-60min，得到分散均匀的料浆；
3）将步骤2）得到的浆料利用增材制造设备打印成一定形状的坯体；
4）将步骤3）得到的坯体置于光固化箱或真空固化箱中二次固化（10min-30min）
5）将步骤4）二次固化的坯体置于管式炉，通入氮气或氩气，并以1-5℃/min的升温速率，从室温加热到200-250℃，保温1-2h，再以 1-5℃/min的升温速率升温到300-400℃并保温1-2h，然后以2-5℃/min的升温速率升温至900℃-1200℃，保温1-2h，随炉冷却至室温，取出得到陶瓷微球增强先驱体陶瓷的结构件。
优选的，所述有机硅先驱体为聚碳硅烷、聚氮硅烷、聚硼硅烷、聚硅氧烷中的一种或多种。
优选的，所述陶瓷微球为SiCO、SiCN、SiBCN、SiOC、SiO2中的一种。
优选的，所述单体为1，6-己二醇二丙烯酸酯、1，4-己二醇二丙烯酸酯、三丙二醇二丙烯酸酯、丙烯酸羟乙酯、三羟甲基丙烷三丙烯酸酯、双季戊四醇六丙烯酸酯、季戊四醇丙烯酸酯中的一种或多种。
优选的，所述光引发剂为2，4，6-三甲基苯甲酰基-二苯基氧化膦、2、4、6-三甲基苯甲酰基苯基膦酸乙酯，苯基双（2，4，6-三甲基苯甲酰基）氧化膦、2-苯基苄-2-二甲基胺-1-（4-吗啉苄苯基）丁酮中的一种或多种。
优选的，所述分散剂为油酸、BYK410、KOS110、KOS1900中的一种。
优选的，所述增材制造为光固化3D打印、粘结剂喷射成型、直写成型技术中的一种。
附图说明
图1是有机硅先驱体乳液法制备的实施例1中陶瓷微球的微观图。
图2是实施例1中增材制造的坯体（a-d）；热解后的陶瓷微球增强先驱体陶瓷（e-h）。
图3是实施例1中陶瓷微球增强先驱体陶瓷断面的微观图。
实施方式
为了使本发明的内容、技术方案更加明了，下面结合具体实施例对本发明的内容作进一步说明。
实施例
将有机硅先驱体乳液法成球后置于管式炉中，氮气或氩气气氛保护，1000℃热解得到SiCN陶瓷微球；
将有机硅先驱体聚硅乙炔50wt%、1,6-己二醇二丙烯酸酯50wt%、2，4，6-三甲基苯甲酰基-二苯基氧化膦3wt%、分散剂BYK 5wt%在磁力搅拌转速400r/min下搅拌2h，然后加入陶瓷微球（10vol%）继续搅拌2h，超声分散30min，得到分散均匀的料浆；
3）将步骤2）得到的料浆利用光固化3D打印设备打印成一定形状的坯体；
4）将步骤3）得到的坯体置于真空固化箱中二次固化20min；
5）将步骤4）二次固化的坯体置于管式炉，通入氮气或氩气，并以 2℃/min的升温速率，从室温加热到250℃，保温1h，再以 1℃/min的升温速率升温到400℃并保温1h，然后以2℃/min的升温速率升温至1000℃，保温1h，随炉冷却至室温，取出得到陶瓷微球增强先驱体陶瓷的结构件，样品的弯曲强度为79.8MPa。
实施例
将有机硅先驱体乳液法成球后置于管式炉中，氮气或氩气气氛保护，800℃热解得到SiCN陶瓷微球；
2）将有机硅先驱体聚硅乙炔50wt%、1,6-己二醇二丙烯酸酯50wt%、2，4，6-三甲基苯甲酰基-二苯基氧化膦3wt%、分散剂BYK 5wt%在磁力搅拌转速400r/min下搅拌2h，然后加入陶瓷微球（10vol%）继续搅拌2h，超声分散30min，得到分散均匀的料浆；
3）将步骤2）得到的料浆利用光固化3D打印设备打印成一定形状的坯体；
4）将步骤3）得到的坯体置于真空固化箱中二次固化20min；
5）将步骤4）二次固化的坯体置于管式炉，通入氮气或氩气，并以 2℃/min的升温速率，从室温加热到250℃，保温1h，再以 1℃/min的升温速率升温到400℃并保温1h，然后以2℃/min的升温速率升温至1000℃，保温1h，随炉冷却至室温，取出得到陶瓷微球增强先驱体陶瓷的结构件，样品的弯曲强度为72.5MPa。
实施例
1）将有机硅先驱体乳液法成球后置于管式炉中，氮气或氩气气氛保护，1000℃热解得到SiOC陶瓷微球；
2）将有机硅先驱体聚硅乙炔50wt%、1,6-己二醇二丙烯酸酯50wt%、2，4，6-三甲基苯甲酰基-二苯基氧化膦3wt%、分散剂BYK 5wt%在磁力搅拌转速400r/min下搅拌2h，得到分散均匀的料浆；
3）将步骤2）得到的料浆利用光固化3D打印设备打印成一定形状的坯体；
4）将步骤3）得到的坯体置于真空固化箱中二次固化20min；
5）将步骤4）二次固化的坯体置于管式炉，通入氮气或氩气，并以 2℃/min的升温速率，从室温加热到250℃，保温1h，再以 1℃/min的升温速率升温到400℃并保温1h，然后以2℃/min的升温速率升温至1000℃，保温1h，随炉冷却至室温，取出得到先驱体陶瓷的结构件，样品的弯曲强度为41.3MPa。
实施例
将有机硅先驱体乳液法成球后置于管式炉中，氮气或氩气气氛保护，1000℃热解得到SiOC陶瓷微球；
2）将有机硅先驱体聚硅乙炔60wt%、1,6-己二醇二丙烯酸酯40wt%、2，4，6-三甲基苯甲酰基-二苯基氧化膦3wt%、分散剂BYK 5wt%在磁力搅拌转速400r/min下搅拌2h，然后加入陶瓷微球（10vol%）继续搅拌2h，超声分散30min，得到分散均匀的料浆；
3）将步骤2）得到的料浆利用光固化3D打印设备打印成一定形状的坯体；
4）将步骤3）得到的坯体置于真空固化箱中二次固化20min；
5）将步骤4）二次固化的坯体置于管式炉，通入氮气或氩气，并以2℃/min的升温速率，从室温加热到250℃，保温1h，再以 1℃/min的升温速率升温到400℃并保温1h，然后以2℃/min的升温速率升温至1000℃，保温1h，随炉冷却至室温，取出得到陶瓷微球增强先驱体陶瓷的结构件，样品的弯曲强度为70.2MPa。
本发明还提供一种应用上述方法制备的先驱体复合陶瓷，本实施例作为一种优选方案，采用光固化3D打印和先驱体转化法结合制得性能优良的陶瓷微球增强先驱体复合陶瓷结构件。
以上实施例仅用以说明本发明的技术方案，而非对其限制；基于本发明的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。
Claims (7)
1.一种增材制造陶瓷微球增强先驱体陶瓷的方法，其特征在于，包括如下具体步骤：
1）将有机硅先驱体乳液法成球后置于管式炉中，氮气或氩气气氛保护，800-1000℃热解得到陶瓷微球；
2）将有机硅先驱体(50wt%-90wt%)、单体(10wt%-50wt%)、光引发剂（1wt%-5wt%）、步骤1）和分散剂（1wt%-5wt%）在磁力搅拌转速400-500r/min下搅拌2-6h，然后加入陶瓷微球（10vol%-60vol%）继续搅拌2-4h，超声分散30-60min，得到分散均匀的料浆；
3）将步骤2）得到的料浆利用增材制造设备打印成一定形状的坯体；
4）将步骤3）得到的坯体置于光固化箱或是真空固化箱中二次固化（10min-30min）
5）将步骤4）二次固化的坯体置于管式炉，通入氮气或氩气，并以1-5℃/min的升温速率，从室温加热到200-250℃，保温1-2h，再以 1-5℃/min的升温速率升温到300-400℃并保温1-2h，然后以2-5℃/min的升温速率升温至900℃-1200℃，保温1-2h，随炉冷却至室温，取出得到陶瓷微球增强先驱体陶瓷的结构件。
2.根据权利要求书1所述的增材制造陶瓷微球增强先驱体陶瓷的方法，其特征在于，步骤1）、2）中所述的有机硅先驱体为聚碳硅烷、聚氮硅烷、聚硼硅烷、聚硅氧烷中的一种。
3.根据权利要求书1所述的增材制造陶瓷微球增强先驱体陶瓷的方法，其特征在于，步骤1）所述的陶瓷微球为SiCO、SiCN、SiBCN、SiOC、SiO2中的一种。
4.根据权利要求书1所述的增材制造陶瓷微球增强先驱体陶瓷的方法，其特征在于，步骤2）中所述的单体为1，6-己二醇二丙烯酸酯、1，4-己二醇二丙烯酸酯、三丙二醇二丙烯酸酯、丙烯酸羟乙酯、三羟甲基丙烷三丙烯酸酯、双季戊四醇六丙烯酸酯、季戊四醇丙烯酸酯中的一种或多种。
5.根据权利要求书1所述的增材制造陶瓷微球增强先驱体陶瓷的方法，其特征在于，步骤2）中所述的光引发剂为2，4，6-三甲基苯甲酰基-二苯基氧化膦、2、4、6-三甲基苯甲酰基苯基膦酸乙酯，苯基双（2，4，6-三甲基苯甲酰基）氧化膦、2-苯基苄-2-二甲基胺-1-（4-吗啉苄苯基）丁酮中的一种或多种。
6.根据权利要求书1所述的增材制造陶瓷微球增强先驱体陶瓷的方法，其特征在于，步骤2）中所述的分散剂为油酸、BYK410、KOS110、KOS1900中的一种。
7.根据权利要求书1所述的增材制造陶瓷微球增强先驱体陶瓷的方法，其特征在于，步骤3）中所述增材制造为光固化3D打印、粘结剂喷射成型、直写成型技术中的一种。
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