CN110028312B - 一种耐高温陶瓷前驱体浆料及其制备方法 - Google Patents

一种耐高温陶瓷前驱体浆料及其制备方法 Download PDF

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CN110028312B
CN110028312B CN201910338520.6A CN201910338520A CN110028312B CN 110028312 B CN110028312 B CN 110028312B CN 201910338520 A CN201910338520 A CN 201910338520A CN 110028312 B CN110028312 B CN 110028312B
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马小民
王慧
崔吟雪
张德育
李富萍
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Guozhuang New Material Technology Jiangsu Co ltd
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Abstract

本发明公开了一种耐高温陶瓷前驱体浆料及其制备方法。所述制备方法包括：步骤(1)将线形有机硅齐聚物充分溶解在有机溶剂中；(2)在加入一定量的陶瓷前驱体，均匀分散；(3)加入催化剂，反应一定时间，制备得到耐高温陶瓷前驱体浆料。本发明制备得到的耐高温陶瓷前驱体浆料主体结构丰富，包括氧化铝、氧化锆、氮化硼、碳化硅等耐高温陶瓷，其纳米颗粒表面化学键合上有机硅聚合物，因而形成稳定的分散液即浆料，该浆料可刷涂、喷涂、滚涂于各种基材表面，用于制备耐高温、高力学强度的陶瓷防护层。

Description

一种耐高温陶瓷前驱体浆料及其制备方法
技术领域
本发明属于陶瓷前驱体领域，尤其涉及一种耐高温陶瓷前驱体浆料及其制备方法。
背景技术
陶瓷是指用天然或合成化合物经过成形、高温烧结等过程制成的一类无机非金属材料。具有高熔点、高硬度、高耐磨性、耐氧化等优点。可用作发动机在内的各种热机材料、电池发电部件材料、核聚变反应堆护壁材料、无公害的外燃式发动机材料等。与高性能分子材料、新金属材料、复合材料并列为四大新材料。
除此之外，陶瓷材料还具有独特的力学、热学、电学、化学和光学特性。作为结构陶瓷的典型代表材料，基于氧化铝、氮化硅、碳化硅的陶瓷具有优异的耐高温性，被广泛应用于火箭尾喷管喷嘴、热电偶套管、炉管等高温下工作的部件、高温下的热交换器材料、以及高硬度和耐磨性制作砂轮、磨料等。为了进一步实现对结构陶瓷性能的调控和优化，研究人员作了大量陶瓷结构与性能之间的关系研究，得出内部微结构(微晶晶面作用，多孔多相分布情况)对力学性能的关系，陶瓷材料性能(如光，电，热，磁)和成形的关系，以及粒度分布，胶着界面的关系也得到发展。然而，陶瓷前驱体通常需经进一步加工、纺丝或热压等工序进一步加工成陶瓷块体、纤维等。对于一些异型件的陶瓷涂层改性，传统的陶瓷前驱体往往达不到预期目的。因此，新型可供各种界面改性用的陶瓷前驱体的设计与合成本领域的难点。
发明内容
针对现有技术的不足和材料的局限性，本发明的主要目的在于提供一种耐高温陶瓷前驱体浆料及其制备方法。
本发明的增益效果为：(1)将陶瓷前驱体做成了浆料形式：通过结构设计合成一种线形有机硅聚合物短链(齐聚物)与无机非金属氧化物纳米颗粒形成的核-壳结构溶胶，该纳米颗粒可稳定分散在溶剂当中，使该浆料具有优异的稳定性；(2)该陶瓷前驱体浆料不仅可以用于溶胶-凝胶纺丝制备陶瓷纤维，或则干燥后压制成型制备陶瓷结构件，而且还可以直接喷涂、刷涂、或滚涂在其他物体表面进行陶瓷涂层改性，且改性物体的表面平整度以及形状都不影响喷涂效果。
为实现前述发明目的，本发明采用的技术方案包括：
本发明提供了一种耐高温陶瓷前驱体浆料及其制备方法，包括三个关键步骤：
(1)将线形有机硅齐聚物充分溶解在有机溶剂中；
(2)在加入一定量的陶瓷前驱体，均匀分散；
(3)加入催化剂，反应一定时间，制备得到耐高温陶瓷前驱体浆料。
本发明实施例还提供了一种耐高温陶瓷前驱体浆料，该浆料主体结构丰富，包括氧化铝、氧化锆、氮化硼、碳化硅等耐高温陶瓷，其纳米颗粒表面化学键合上有机硅聚合物，因而形成稳定的分散液即浆料，该浆料可刷涂、喷涂、滚涂于各种基材表面，用于制备耐高温、耐腐蚀、高力学强度的陶瓷防护层。
附图说明
图1为本发明实施列1-6中所获耐高温陶瓷驱体浆料的结构示意图；
图2为本发明实施列1中所获耐高温陶瓷前驱体浆料的透射电镜图；
图3为本发明实施例2中所获耐高温陶瓷前驱体浆料的透射电镜图；
图4为本发明实施例3中所获耐高温陶瓷前驱体浆料的透射电镜图；
图5为本发明实施例4中所获耐高温陶瓷前驱体浆料的透射电镜图；
图6为本发明实施例5中所获耐高温陶瓷前驱体浆料的透射电镜图；
图7为本发明实施例6中所获耐高温陶瓷前驱体浆料的透射电镜图。
具体实施方式
鉴于现有技术中的不足，本案发明人经长期研究和大量实践，得以提出本发明的技术方案。首先提供了一种耐高温陶瓷驱体浆料及其制备方法。
本发明实施例的一个方面提供了一种耐高温陶瓷驱体浆料的制备方法，包括三个关键步骤：
(1)将线形有机硅齐聚物充分溶解在有机溶剂中；
(2)在加入一定量的陶瓷前驱体，均匀分散；
(3)加入催化剂，反应一定时间，制备得到耐高温陶瓷前驱体浆料。
在一些实施例中，所述有机硅烷齐聚物包括聚二乙氧基硅氧烷，聚二甲氧基硅氧烷，聚甲基乙氧基硅氧烷，聚甲基甲氧基硅氧烷，聚己基乙氧基硅氧烷，聚己基甲氧基硅氧烷，烷氧基硅氧烷共聚物，且不限于此。
进一步地，所述有机硅聚合物的重复单元为5-20。
进一步地，所述溶剂包括甲醇、乙醇、异丙醇、丙醇、丁醇，叔丁醇，正己烷，四氢呋喃，N-甲基吡咯烷酮，丙酮，二甲基亚砜，N，N-二甲基甲酰胺，且不限于此。
进一步地，所述溶剂用量为有机硅聚合物的10倍以上。
在一些实施例中，所述陶瓷前驱体包括铝粉、氯化铝、硫酸铝、硝酸铝、硅酸铝、硫化铝、异丙醇铝、九水硝酸铝、氧化锆、烷氧基锆、异丙醇锆、氢氧化锆、氮化硼、聚硅碳烷、聚硅碳氮烷、聚硅碳硼烷的任意一种或两种以上的组合，且不限于此。
进一步地，所述陶瓷前驱体与有机硅齐聚物的摩尔比大于10∶1。
进一步地，所述催化剂包括氢氧化钠、氢氧化钾、尿素、氨水、吡啶、三甲基氯化铵、和三乙胺中的任意一种或两种以上的组合，且不限于此。
进一步地，所述催化剂与有机硅齐聚物的摩尔比为0.01∶1～0.1∶1。
进一步地，所述反应温度为室温至80℃。
进一步地，所述反应时间为3～10小时。
以下通过若干实施例并结合附图进一步详细说明本发明的技术方案。然而，所选的实施例仅用于说明本发明，而不限制本发明的范围。
实施例1
(1)取1mol平均重复单元数为5的聚二乙氧基硅氧烷，充分溶解在12mol甲醇当中，剧烈搅拌，形成均一的溶液；
(2)向上述溶液中加入8mol的铝粉、2mol的九水硝酸铝和5mol的硅酸铝，充分搅拌，形成复合分散溶液；
(3)向以上复合溶液中加入0.01mol的氢氧化钾，在室温条件下搅拌10小时，聚二乙氧基硅氧烷水解，并与铝粉和九水硝酸铝发生缩聚反应，获得稳定的耐高温陶瓷前驱体浆料，该浆料的结构示意图参见图1，干燥后前驱体纳米颗粒形貌参见透射电镜图2。
实施例2
(1)取1mol平均重复单元数为8的聚二甲氧基硅氧烷，充分溶解在15mol丁醇中，剧烈搅拌，形成均一的溶液；
(2)向上述溶液中加入10mol的氯化铝、3mol的硫酸铝、2mol的硝酸铝，充分搅拌，形成复合分散溶液；
(3)向以上复合溶液中加入0.03mol的氨水，在40℃条件下搅拌8小时，聚二甲氧基硅氧烷水解，并与氯化铝、硫酸铝、硝酸铝发生缩聚反应，获得稳定的耐高温陶瓷前驱体浆料，该浆料的结构示意图参见图1，干燥后前驱体纳米颗粒形貌参见透射电镜图3。
实施例3
(1)取1mol平均重复单元数为12的聚甲基乙氧基硅氧烷，充分溶解在13mol的二甲基亚砜中，剧烈搅拌，形成均一的溶液；
(2)向上述溶液中加入10mol的氢氧化锆和2mol的硝酸铝，充分搅拌，形成复合分散溶液；
(3)向以上复合溶液中加入0.08mol的吡啶，在50℃下搅拌6小时，聚甲基乙氧基硅氧烷水解，并与氢氧化锆、硝酸铝发生缩聚反应，获得稳定的耐高温陶瓷前驱体浆料，该浆料的结构示意图参见图1，干燥后前驱体纳米颗粒形貌参见透射电镜图4。
实施例4
(1)取1mol平均重复单元数为18的聚甲基甲氧基硅氧烷，充分溶解在15mol N-甲基吡咯烷酮中，剧烈搅拌，形成均一的溶液；
(2)向上述溶液中加入10mol的氮化硼和2mol的聚硅碳烷，充分搅拌，形成复合分散溶液；
(3)向以上复合溶液中加入0.08mol的吡啶，在60℃下搅拌5小时，聚甲基甲氧基硅氧烷水解，并与氮化硼、聚硅碳烷发生缩聚反应，获得稳定的耐高温陶瓷前驱体浆料，该浆料的结构示意图参见图1，干燥后前驱体纳米颗粒形貌参见透射电镜图5。
实施例5
(1)取1mol平均重复单元数为20的聚己基乙氧基硅氧烷，充分溶解在12mol的甲醇中，剧烈搅拌，形成均一的溶液；
(2)向上述溶液中加入10mol的聚硅碳氮烷和2mol的聚硅碳氮烷，充分搅拌，形成复合分散溶液；
(3)向以上复合溶液中加入0.08mol的三乙胺，在80℃下搅拌3小时，聚己基乙氧基硅氧烷水解，并与聚硅碳氮烷、聚硅碳氮烷发生缩聚反应，获得稳定的耐高温陶瓷前驱体浆料，该浆料的结构示意图参见图1，干燥后前驱体纳米颗粒形貌参见透射电镜图6。
实施例6
(1)取1mol平均重复单元数为18的聚己基甲氧基硅氧烷，充分溶解在14mol的叔丁醇中，剧烈搅拌，形成均一的溶液；
(2)向上述溶液中加入10mol的铝粉和5mol的九水硝酸铝，充分搅拌，形成复合分散溶液；
(3)向以上复合溶液中加入0.05mol的氢氧化钠，在70℃下搅拌4小时，聚聚己基甲氧基硅氧烷水解，并与铝粉、九水硝酸铝发生缩聚反应，获得稳定的耐高温陶瓷前驱体浆料，该浆料的结构示意图参见图1，干燥后前驱体纳米颗粒形貌参见透射电镜图7。
应当理解，以上所述的仅是本发明的一些实施方式，应当指出，对于本领域的普通技术人员来说，在不脱离本发明的创造构思的前提下，还可以做出其它变形和改进，这些都属于本发明的保护范围。

Claims (7)

1.一种耐高温陶瓷，其特征在于，前驱体浆料的制备方法包括以下三个关键步骤：(1)将线形有机硅齐聚物充分溶解在有机溶剂中；(2)在加入一定量的陶瓷前驱体，均匀分散；(3)加入催化剂，反应一定时间，制备得到耐高温陶瓷前驱体浆料；
步骤(1)所述线形有机硅齐聚物包括聚二乙氧基硅氧烷，聚二甲氧基硅氧烷，聚甲基乙氧基硅氧烷，聚甲基甲氧基硅氧烷，聚己基乙氧基硅氧烷，聚己基甲氧基硅氧烷，烷氧基硅氧烷共聚物的任意一种或两种以上的组合；所述有机硅聚合物的重复单元为5-20；
步骤(2)所述陶瓷前驱体包括铝粉、氯化铝、硫酸铝、硝酸铝、硅酸铝、硫化铝、异丙醇铝、九水硝酸铝、氧化锆、烷氧基锆、异丙醇锆、氢氧化锆、氮化硼、聚硅碳烷、聚硅碳氮烷、聚硅碳硼烷的任意一种或两种以上的组合；
步骤(3)所述催化剂包括：氢氧化钠、氢氧化钾、尿素、氨水、吡啶、三甲基氯化铵、和三乙胺中的任意一种或两种以上的组合。
2.根据权利要求1所述一种耐高温陶瓷，其特征在于，步骤(1)所述有机溶剂包括甲醇、乙醇、异丙醇、丙醇、丁醇，叔丁醇，正己烷，四氢呋喃，N-甲基吡咯烷酮，丙酮，二甲基亚砜，N，N-二甲基甲酰胺的任意一种或两种以上的组合；所用溶剂用量为有机硅聚合物的10倍以上。
3.根据权利要求1所述一种耐高温陶瓷，其特征在于，所述陶瓷前驱体与有机硅齐聚物的摩尔比大于10∶1。
4.根据权利要求1所述一种耐高温陶瓷，其特征在于,步骤(3)所述催化剂与有机硅齐聚物的摩尔比为0.01∶1～0.1∶1。
5.根据权利要求1所述一种耐高温陶瓷，其特征在于,步骤(3)所述反应温度为室温至80℃。
6.根据权利要求1所述一种耐高温陶瓷，其特征在于,步骤(3)所述反应时间为3～10小时。
7.根据权利要求1所述耐高温陶瓷的应用，其特征在于，所得浆料经刷涂、喷涂、滚涂于基材表面，用于制备耐高温、耐腐蚀、高力学强度的陶瓷防护层。
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