CN110204313B - 一种分散剂交联原位凝固陶瓷悬浮体的方法及陶瓷成型方法 - Google Patents

一种分散剂交联原位凝固陶瓷悬浮体的方法及陶瓷成型方法 Download PDF

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CN110204313B
CN110204313B CN201810167433.4A CN201810167433A CN110204313B CN 110204313 B CN110204313 B CN 110204313B CN 201810167433 A CN201810167433 A CN 201810167433A CN 110204313 B CN110204313 B CN 110204313B
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杨金龙
干科
盖艳娇
刘静静
鲁毓钜
张笑妍
席小庆
任博
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Tsinghua University
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Abstract

本发明公开一种分散剂交联原位凝固陶瓷悬浮体的方法及陶瓷成型方法，属于无机非金属陶瓷悬浮体固化技术领域。本发明方法通过添加固化剂引发分散剂发生交联反应，以实现陶瓷悬浮体的原位凝固。本发明方法以有机磺酸酯和纤维素为固化剂，通过外部可控条件，使固化剂引发或直接与分散剂发生交联反应，实现陶瓷悬浮体的原位固化，并通过分散剂的交联，在陶瓷坯体中形成三维网络结构，有效的提高了坯体的力学性能，改善了直接凝固注模成型和分散剂反应失效注模成型，制备陶瓷坯体强度较低的缺陷，使其能够满足后期机加工过程，更加适用于规模化工业生产。

Description

一种分散剂交联原位凝固陶瓷悬浮体的方法及陶瓷成型方法
技术领域
本发明涉及无机非金属陶瓷悬浮体固化技术领域，特别涉及一种分散剂交联原位凝固陶瓷悬浮体提高坯体强度的成型方法。
背景技术
陶瓷分散剂失效原位凝固注模成型(Dispersion removal coagulationcasting,DRCC)是近年来提出的一种新型陶瓷胶态成型工艺。其固化原理是：通过外部自由可控条件(如温度、pH值、压力等)，利用分散剂的反应活性，或本征物理特性，使悬浮体中的分散剂以反应、水解、析出等方式失去分散效果，降低陶瓷颗粒间的静电排斥力，或者从陶瓷颗粒表面脱附，导致悬浮体失稳而发生原位固化。该方法对于高固相含量水基和非水基陶瓷悬浮体均适用，被广泛应用于氧化铝、氧化锆等氧化物陶瓷悬浮体，氮化硅、碳化硅等非氧化物陶瓷悬浮体，以及钛酸锶钡、锆钛酸铅等压电、铁电陶瓷悬浮体的固化。
为此，中国专利文献CN103922757A和CN106565248A中分别公开了以四甲基氢氧化铵和聚磷酸盐为分散剂的失效固化陶瓷悬浮体的方法。由于这两种方法中固化时，依靠陶瓷粉体之间的范德华吸引力使颗粒实现团聚，但静电排斥力并未完全消除，所以固化后得到的陶瓷坯体强度不高，无法满足后期机加工过程。专利CN106866123A公开了一种低温诱导分散剂失效固化陶瓷悬浮体的方法。该方法适用于非水基陶瓷悬浮体，但是固化时间较长，不利于工业化生产。
发明内容
因此，为了克服现有直接凝固注模成型、陶瓷分散剂反应失效原位凝固注模成型方法中，陶瓷坯体强度低以及固化时间较长，不利于工业化生产的缺点，本发明提供一种分散剂交联固化陶瓷悬浮体提高坯体强度的方法。
为此，本发明提供以下技术方案：
一种分散剂交联失效原位固化陶瓷悬浮体的方法，通过外部可控条件，使固化剂引发或直接与分散剂发生交联反应，实现陶瓷悬浮体的原位固化，并通过分散剂的交联，在陶瓷坯体中形成三维网络结构，有效的提高了坯体的力学性能。
制备所述陶瓷悬浮体所采用的陶瓷粉体为氧化铝、氧化锆、氧化硅、氮化硅、碳化硅、硼化锆中的一种或几种所述分散剂为聚乙烯吡咯烷酮或聚乙烯亚胺，其分子量为10000、30000、50000、70000、90000中的一种或几种。
所述固化剂为机磺酸酯或纤维素类物质；当所述分散剂为聚乙烯吡咯烷酮时，所述固化剂为机磺酸酯；
当所述分散剂为聚乙烯亚胺时，所述固化剂为纤维素类物质；
所述纤维素类物质以质量分数为2～5％的水溶液添加。
所述机磺酸酯为硫酸二甲酯、硫酸二乙酯、硫酸二异丙酯中的一种或几种；所述纤维素类物质为甲基纤维素、羧甲基纤维素、羟乙基纤维素中的一种或几种。所述固化剂的用量为悬浮体体积分数的1～5％。
将陶瓷粉体、水与分散剂混合球磨均匀，制备固相体积含量为50～55％的陶瓷悬浮体，其中分散剂占陶瓷粉体质量的0.1％～1.0％；然后加入固化剂搅拌均匀，注模、脱模，干燥，烧结。
一种陶瓷成型方法，具体步骤如下：
(1)将陶瓷粉体、水与分散剂混合并球磨均匀，制备固相体积含量为50～55％的陶瓷悬浮体，其中分散剂占陶瓷粉体质量的0.05％～1.0％；
(2)将步骤(1)所述陶瓷悬浮体在真空条件下搅拌除去气泡，在室温条件下或加热至40℃添加固化剂搅拌均匀；
(3)将步骤(2)所述陶瓷悬浮体注入无孔模具中，在不同温度下水浴处理脱模获得陶瓷湿坯，在80～100℃的条件下干燥24～48小时得到干坯。
(4)将步骤(3)中得到的干坯置于烧结炉中以每分钟5～8℃的升温速率升温至1450～1950℃保温2～5小时得到陶瓷烧结体。其中，非氧化物陶瓷在真空及特定气氛条件下烧结。
所述球磨时间为12～48小时。
所述真空搅拌时间为10～30分钟。
所述无孔模具材料为金属、塑料、玻璃、橡胶中的任何一种。
所述水浴加热温度为60～80℃，时间为15～120分钟。
本领域中，常用聚合物和聚合物电解质作为陶瓷粉体的分散剂，聚乙烯吡咯烷酮(PVP)和聚乙烯亚胺(PEI)是常用的聚合物分散剂。其中聚乙烯吡咯烷酮的聚合度较高，分子量可高达8000～700000，它可以一端锚固在陶瓷颗粒表面，利用较长的分子链，另一段游离在溶剂中，实现陶瓷悬浮体的空间位阻稳定；同时聚乙烯吡咯烷酮可以在过硫酸盐或硫酸根等的引发下，发生进一步的交联反应，形成更高聚合度的PVPP结构，使游离在溶剂中的一端交联在一起，从而使得悬浮体失去原本的空间位阻作用，实现原位凝固。聚乙烯亚胺是聚合物电解质，其不仅可以锚固在陶瓷颗粒表面，实现陶瓷悬浮体的空间位阻稳定，还可以吸附在陶瓷粉体表面，增大颗粒间的静电排斥力，实现陶瓷悬浮体的静电空间位阻稳定。由于聚乙烯亚胺的分子链中包含许多反应活性很强的伯胺(-NH)和仲胺(-NH2)的亚胺结构，导致聚乙烯亚胺也具有较强的反应活性，其可以与纤维素类物质上的羟基发生反应形成交联。所以我们可以向陶瓷悬浮体中添加纤维素类物质作为固化剂，通过控制外部条件(如温度、pH值等)，使其与分散剂聚乙烯亚胺发生交联反应，从而使得陶瓷悬浮体失去原本的静电空间位阻作用，实现原位凝固。
本发明方法与现有技术相比具有如下优点：
1、本发明提供的分散剂交联原位凝固陶瓷悬浮体的方法以有机磺酸酯和纤维素为固化剂，通过外部可控条件，使固化剂引发分散剂发生自交联或直接与分散剂发生交联反应，使悬浮体失去分散效果，从而实现陶瓷悬浮体的原位凝固，分散剂交联之后在坯体中形成的三维网络结构能够有效的提高坯体的力学性能。
2、本发明提供的分散剂交联原位凝固陶瓷悬浮体的方法通过添加固化剂引发或直接与分散剂发生交联反应，实现陶瓷悬浮体的原位固化，并通过分散剂的交联，在陶瓷坯体中形成三维网络结构，有效的提高了坯体的力学性能，改善了直接凝固注模成型和分散剂失效原位凝固注模成型中，制备陶瓷坯体强度较低的缺陷，使其能够满足后期机加工过程。
3、本发明提供的分散剂交联原位凝固陶瓷悬浮体的方法采用分散剂形成交联，分散剂交联后在坯体中形成的三维网络结构，可以有效的提高陶瓷坯体的力学性能，满足后期机加工过程，较凝胶注模成型中有机添加剂少，更加适用于规模化工业生产。
4、本发明提供的陶瓷成型方法可成型各种复杂形状和大小的陶瓷部件；可广泛应用于各类陶瓷体系的固化及陶瓷部件制备。
具体实施方式
提供下述实施例是为了更好地进一步理解本发明，并不局限于所述最佳实施方式，不对本发明的内容和保护范围构成限制，任何人在本发明的启示下或是将本发明与其他现有技术的特征进行组合而得出的任何与本发明相同或相近似的产品，均落在本发明的保护范围之内。
实施例中未注明具体实验步骤或条件者，按照本领域内的文献所描述的常规实验步骤的操作或条件即可进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规试剂产品。
实施实例1.
以硫酸二甲酯为固化剂，原位凝固聚乙烯吡咯烷酮分散的氧化铝陶瓷悬浮体。
将1.464克聚乙烯吡咯烷酮、488克氧化铝与100克水混合，球磨24小时后制备得固相体积分数为55％的氧化铝陶瓷悬浮体。将氧化铝陶瓷悬浮体置于40℃水浴中保持15分钟后，添加3毫升硫酸二甲酯，真空搅拌10分钟除去气泡，注入塑料模具中，在70℃下继续水浴处理1小时后脱模获得湿坯，在100℃下干燥24小时获得干坯，以每分钟5℃的升温速率升温至1550℃，保温2个小时，获得氧化铝陶瓷。其中，湿坯的抗压强度为6.34±1.1MPa，陶瓷的抗弯强度为488±42MPa，韦伯模数为22。
实施实例2.
以硫酸二乙酯为固化剂，原位凝固聚乙烯吡咯烷酮分散的氧化锆陶瓷悬浮体。
将1.22克聚乙烯吡咯烷酮、610克氧化锆与100克水混合，球磨24小时后制备得固相体积分数为50％的氧化锆陶瓷悬浮体。将氧化锆陶瓷悬浮体置于40℃水浴中保持15分钟后，添加4毫升硫酸二乙酯，注入橡胶模具中，在50℃下水浴处理2小时后脱模获得湿坯，在80℃下干燥48小时获得干坯，以每分钟7℃的升温速率升温至1450℃，保温4个小时，获得氧化锆陶瓷。其中，湿坯的抗压强度为6.9±0.9MPa，陶瓷的抗弯强度为920±90MPa，韦伯模数为15。
实施实例3.
以硫酸二异丙酯为固化剂，原位凝固聚乙烯吡咯烷酮分散的氧化硅陶瓷悬浮体。
将0.795克聚乙烯吡咯烷酮、265克氧化硅与100克水混合，球磨24小时后制备得固相体积分数为50％的氧化锆陶瓷悬浮体。将氧化硅陶瓷悬浮体置于40℃水浴中保持30分钟后，添加2毫升硫酸二异丙酯，注入橡胶模具中，在60℃下水浴处理0.5小时后脱模获得湿坯，在80℃下干燥48小时获得干坯，以每分钟7℃的升温速率升温至1270℃，保温4个小时，获得氧化硅陶瓷。其中，湿坯的抗压强度为5.9±0.7MPa，陶瓷的抗弯强度为138±47MPa，韦伯模数为17。
实施实例4.
以甲基纤维素为固化剂，原位凝固聚乙烯亚胺分散的氮化硅陶瓷悬浮体。
将6.4克质量分数为10％的聚乙烯亚胺水溶液、320克氮化硅与94.2克水混合球磨48小时后制备得固相体积分数为50％的氮化硅陶瓷悬浮体。向氮化硅陶瓷悬浮体中添加2毫升质量分数为3％的甲基纤维素水溶液。真空搅拌30分钟除去气泡，注入玻璃模具中，在70℃下水浴处理1小时后脱模获得湿坯，在100℃下干燥24小时获得干坯，以每分钟8℃的升温速率升温至1850℃，保温2个小时，且气氛为氮气，获得氮化硅陶瓷。其中，湿坯的抗压强度为2.1±0.4MPa，陶瓷的抗弯强度为790±66MPa，韦伯模数为20。
实施实例5.
以羧甲基纤维素为固化剂，原位凝固聚乙烯亚胺分散的硼化锆陶瓷悬浮体。
将18.24克质量分数为10％的聚乙烯亚胺水溶液、608克硼化锆与83.6克水混合，球磨36小时后制备得固相体积分数为50％的硼化锆陶瓷悬浮体。向硼化锆瓷悬浮体中添加3毫升质量分数为3％的羧甲基纤维素水溶液。真空搅拌20分钟除去气泡，注入橡胶模具中，在60℃下水浴处理2小时后脱模获得湿坯，在100℃下干燥24小时获得干坯，在真空条件下以每分钟6℃的升温速率升温至1900℃，保温5个小时，获得硼化锆陶瓷。其中，湿坯的抗压强度为2.5±0.5MPa，陶瓷的抗弯强度为805±72MPa，韦伯模数为18。
实施实例6.
以羟乙基纤维素为固化剂，原位凝固聚乙烯亚胺分散的碳化硅陶瓷悬浮体。
将18.24克质量分数为10％的聚乙烯亚胺水溶液、332克碳化硅与100克水混合，球磨24小时后制备得固相体积分数为52％的碳化硅陶瓷悬浮体。向碳化硅瓷悬浮体中添加2毫升质量分数为3％的羟乙基纤维素水溶液。真空搅拌15分钟除去气泡，注入金属模具中，在70℃下水浴处理1.5小时后脱模获得湿坯，在90℃下干燥36小时获得干坯，以每分钟5℃的升温速率升温至1950℃，保温3个小时，获得碳化硅陶瓷。其中，湿坯的抗压强度为2.0±0.6MPa，陶瓷的抗弯强度为721±32MPa，韦伯模数为28。
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。

Claims (7)

1.一种分散剂交联原位凝固陶瓷悬浮体的方法，其特征在于，添加固化剂引发分散剂发生交联反应，以实现陶瓷悬浮体的原位凝固；所述分散剂为聚乙烯吡咯烷酮或聚乙烯亚胺；所述固化剂为有 机磺酸酯或纤维素类物质；
当所述分散剂为聚乙烯吡咯烷酮时，所述固化剂为有机磺酸酯；当所述分散剂为聚乙烯亚胺时，所述固化剂为纤维素类物质。
2.根据权利要求1所述的方法，其特征在于：制备所述陶瓷悬浮体所采用的陶瓷粉体为氧化铝、氧化锆、氧化硅、氮化硅、碳化硅、硼化锆中的一种或几种。
3.根据权利要求2所述的方法，其特征在于：所述分散剂的分子量为10000、30000、50000、70000、90000中的一种或几种。
4.根据权利要求1所述的方法，其特征在于：
所述纤维素类物质以质量分数为2～5％的水溶液添加。
5.根据权利要求4所述的方法，其特征在于：所述有机磺酸酯为硫酸二甲酯、硫酸二乙酯、硫酸二异丙酯中的一种或几种；所述纤维素类物质为甲基纤维素、羧甲基纤维素、羟乙基纤维素中的一种或几种。
6.根据权利要求1-5任一所述的方法，其特征在于：所述固化剂的用量为悬浮体体积分数的1～5％。
7.根据权利要求6所述的方法，其特征在于：将陶瓷粉体、水与分散剂混合球磨均匀，制备固相体积含量为50～55％的陶瓷悬浮体，其中分散剂占陶瓷粉体质量的0.1％～1.0％；然后加入固化剂搅拌均匀，注模、脱模，干燥，烧结。
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