CN110330329A - 一种用于立体光刻成型的触变性陶瓷膏体材料及其制备方法 - Google Patents

一种用于立体光刻成型的触变性陶瓷膏体材料及其制备方法 Download PDF

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CN110330329A
CN110330329A CN201910265201.7A CN201910265201A CN110330329A CN 110330329 A CN110330329 A CN 110330329A CN 201910265201 A CN201910265201 A CN 201910265201A CN 110330329 A CN110330329 A CN 110330329A
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thixotropy
stereolithography
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戴红莲
黄孝龙
马遇乐
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Wuhan University of Technology WUT
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Abstract

本发明涉及一种用于立体光刻成型的触变性陶瓷膏体材料及其制备方法，按照质量百分比计，主要包括70‑85wt％的陶瓷粉体；3‑15wt％的触变剂；10‑25wt％的光固化树脂。制备方法主要包括以下步骤：将陶瓷粉体、光固化树脂、分散剂、光引发剂球磨搅拌后加入触变剂继续球磨搅拌后得到膏体。该陶瓷膏体具有固含量高、显著的触变性和屈服假塑性等特点，这极大地方便了成型过程，提高了部件的质量。可用于医疗、航空航天、国防和工业领域。

Description

一种用于立体光刻成型的触变性陶瓷膏体材料及其制备方法
技术领域
本发明属于陶瓷增材制造技术领域，特别涉及一种用于立体光刻成型的触变性陶瓷膏体材料及其制备方法。
背景技术
立体光刻技术(Stereolithography)是在1981年由Hideo Kodama发明的一种快速制造技术。“Stereolithography”一词源自描述三维过程的术语“立体”和“平版印刷术”，意思是将升高或凹陷结构印刷到平面上。基于CAD模型切片数据，通过不同波长的光(可见光、红外光、紫外光等)选择性固化光敏树脂溶液或含有光敏树脂的悬浮液，来逐层构建零件。基于立体光刻技术开发出很多不同增材制造设备，它们的区别主要在光源系统和重涂系统。按分辨率的大小可以分为SLA和μSLA(三个方向的空间分辨率在150μm的范围内)。SL设备一般是基于紫外激光光源，Griffith将这种技术引入到制备陶瓷的领域中，过程与打印树脂的过程类似，一种可聚合的光敏陶瓷悬浮液，包括陶瓷粉体、树脂单体、分散剂、光引发剂等其他助剂，在刮刀的作用下平铺开来，紫外激光根据此层的切片模型选择性固化该层，扫描完成后，重复这个过程，直至打印完零件。
用于陶瓷立体光刻的材料有浆料和膏料，它们的表观区别就是在重力作用下能不能自由流动。国内对于陶瓷立体光刻材料的研究多集中于浆料，如CN106747360A、CN106810215A、CN107129283A、CN105566860A等，但浆料存在无法长期储存、固含量低、支撑复杂等缺点。虽然CN 107500736 A报道了一种膏料及其制备方法，但这种膏料与浆料成分无异，造成其粘度大，难以在刮刀的作用下形成平坦的料层，这对打印工艺造成了极大的困难，且其没有改善支撑复杂的问题，这会损害部件的表面质量。
发明内容
针对以上问题，本发明提出一种用于立体光刻成型的触变性陶瓷膏体材料及其制备方法，所得膏料具有固含量高、可长期储存、易铺平、支撑简单，制备的部件机械性能和表面质量佳。
本发明解决上述技术问题所采用的技术方案是：一种用于立体光刻成型的触变性陶瓷膏体材料，其包括有以下组分，按照质量份数计为，陶瓷粉体70-80wt％；触变剂3-15wt％；光固化树脂10-25wt％；分散剂1-5wt％。
按上述方案，所述的陶瓷粉体为β-磷酸三钙、羟基磷灰石、生物玻璃、氧化铝、氧化镁和氧化锆中的一种或任意两种的混合。
按上述方案，所述的触变剂为气相二氧化硅、聚酰胺蜡、聚乙二醇、琼脂、蓖麻油衍生物、聚烯烃蜡、改性聚脲的N一甲基吡咯烷酮溶液中的一种或多种的混合。
按上述方案，所述的分散剂为磷酸酯、聚丙烯酸铵、聚丙烯酸酯中的一种或两种的混合。
按上述方案，所述的光固化树脂按质量分数由以下组分组成：98-99.5wt％的光固化树脂单体和0.5-2wt％的光引发剂。
按上述方案，所述的光固化树脂单体为丙烯酸月桂酯、三环癸基二甲醇二丙烯酸酯、丙氧基化新戊二醇二丙烯酸酯、烷氧基化季戊四醇四丙烯酸酯、乙氧基化三羟甲基三丙烯酸酯、聚乙二醇二丙烯酸酯、三丙二醇二丙烯酸酯、烷氧基化双酚A二(甲基)丙烯酸酯、甲氧基聚乙二醇(350)单丙烯酸酯、甲氧基丙氧基新戊二醇单丙烯酸酯、1，6-乙二醇二丙烯酸酯中的任意一种或多种的混合。
按上述方案，所述的光引发剂为2-羟基-2-甲基-苯基丙酮-1、1-羟基-环己基苯甲酮、2-羟基-2-甲基-对羟乙基醚基苯基丙酮-1、2,4,6-(三甲基苯甲酰基)二苯氧化膦中的任意一种或多种的混合。
用于立体光刻成型的触变性陶瓷膏体材料的制备方法，其特征在于，包括以下步骤：
a)光固化树脂预混液配置：将所需比例的光固化树脂单体、光引发剂、分散剂加入球磨罐中混合搅拌均匀得到预混液；
b)分步加入所需比例的陶瓷粉体，球磨使其均匀地分散在预混液中；
c)分布加入所需比例的触变剂，球磨得到符合流变性能要求膏体材料。
本发明所得的触变性陶瓷膏体材料的流变性能为屈服假塑性，屈服应力为60Pa-700Pa，低剪切速率(0.01-0.1s-1)下粘度100Pa·s-50000Pa·s，高剪切速率(100s-1)下低粘度1-40Pa·s。
本发明所得的膏料中含有一定的触变剂成分，触变剂作用原理是：触变剂一般是含有大量羟基或酰胺基的物质，经活化(搅拌、球磨)后它在悬浮液中形成氢键网络，大大提高体系的粘度，赋予膏料一定的屈服应力，但由于该网络是通过物理键结合的，很容易在剪切力的作用下断裂，使得体系粘度迅速下降，使其容易刮平，剪切力消失后，氢键网络又会迅速形成，提供支撑作用。
本发明将立体光刻技术用于陶瓷增材制造，与现有的光固化陶瓷原料与制备技术相比具有以下优点：
1)具有固含量高的优势，这将大大减少脱脂和烧结过程中造成的缺陷；
2)具有高的屈服应力和一定的触变性，这将使得支撑不必与打印件相连，可以大大简化去除支撑的时间，并保证好的表面质量。
3)具有显著的剪切稀化效应，这使得膏料在高剪切速率下具有较低的粘度，有利于在刮刀的作用下形成薄而平的层。
附图说明
图1为实施例1的流变性能示意图；
图2为实施例2的流变性能示意图；
图3为实施例3的流变性能示意图；
图4为实施例4的流变性能示意图；
图5为实施例5的流变性能示意图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
实施例1
准备好高能行星球磨机，向球磨罐中依次加入适量大小氧化锆磨球，16g的光固化单体三环癸基二甲醇二丙烯酸酯、0.24g的光引发剂2-羟基-2-甲基-苯基丙酮-1、2.1706g磷酸酯分散剂，搅拌使其混合溶解。分三次称取120gβ-磷酸三钙于球磨罐中，每次称取40g，并依次在200r/min、250r/min、250/min转速下各球磨1h。球磨结束后，往球磨罐中加入8.5g聚乙二醇300触变剂，于300r/min或350r/min转速下球磨2h得到符合要的膏料，如图1，流变性能测试显示该膏体剪切速率为0.01s-1是粘度大于16000pa·s，随着剪切速率增加粘度迅速减少，剪切速率为100s-1是粘度小于20pa·s，屈服应力大于400pa，并有明显的触变环。
实施例2
准备好高能行星球磨机，向球磨罐中依次加入适量大小氧化锆磨球，20g的光固化单体1，6-乙二醇二丙烯酸酯、0.16g的光引发剂2-羟基-2-甲基-苯基丙酮-1、1.2g磷酸酯分散剂，搅拌使其混合溶解。分三次称取48gβ-磷酸三钙和12g生物玻璃粉体于球磨罐中，每次称取16gβ-磷酸三钙和4g生物玻璃粉体，并依次在200r/min、250r/min、250/min转速下各球磨0.5h。球磨结束后，往球磨罐中加入4g疏水型气相二氧化硅触变剂，于300r/min或350r/min转速下球磨2h得到符合要求的膏料。如图2，流变性能测试显示该膏体剪切速率为0.01s-1时粘度大于700pa·s，随着剪切速率增加粘度迅速减少，剪切速率为100s-1时粘度小于7pa·s，屈服应力大于70pa，并有明显的触变环。
实施例3
准备好高能行星球磨机，向球磨罐中依次加入适量大小氧化锆磨球，20g的光固化单体乙氧基化三羟甲基三丙烯酸酯、0.16g的光引发剂2-羟基-2-甲基-苯基丙酮-1、1.05g聚丙烯酸酯，搅拌使其混合溶解。分三次称取70g氧化铝于球磨罐中，每次称取23.3g氧化铝，并依次在200r/min、250r/min、250/min转速下各球磨1h。球磨结束后，往球磨罐中加入2g聚酰胺蜡粉触变剂，于300r/min或350r/min转速下球磨2h得到符合要求的膏料如图3，流变性能测试显示该膏体剪切速率为0.01s-1时粘度大于30000pa·s，随着剪切速率增加粘度迅速减少，剪切速率为100s-1时粘度小于30pa·s，屈服应力大于320pa，并有明显的触变环。
实施例4
准备好高能行星球磨机，向球磨罐中依次加入适量大小氧化锆磨球，20g的光固化单体1，6-乙二醇二丙烯酸酯、0.16g的光引发剂2-羟基-2-甲基-苯基丙酮-1、1.2g磷酸酯分散剂，搅拌使其混合溶解。分三次称取80g氧化镁粉体于球磨罐中，每次称取26.67g，并依次在200r/min、250r/min、250/min转速下各球磨0.5h。球磨结束后，往球磨罐中加入4g蓖麻油衍生物，于300r/min或350r/min转速下球磨2h得到符合要求的膏料。如图4，流变性能测试显示该膏体剪切速率为0.01s-1时粘度大于1300pa·s，随着剪切速率增加粘度迅速减少，剪切速率为100s-1时粘度小于40pa·s，屈服应力大于130pa，并有明显的触变环。
实施例5
准备好高能行星球磨机，向球磨罐中依次加入适量大小氧化锆磨球，20g的光固化单体乙氧基化三羟甲基三丙烯酸酯、0.16g的光引发剂2-羟基-2-甲基-苯基丙酮-1、1.05g聚丙烯酸酯，搅拌使其混合溶解。分三次称取75g氧化锆于球磨罐中，每次称取25g，并依次在200r/min、250r/min、250/min转速下各球磨1h。球磨结束后，往球磨罐中加入2g聚烯烃蜡触变剂，于300r/min或350r/min转速下球磨3h得到符合要求的膏料。如图5，流变性能测试显示该膏体剪切速率为0.01s-1时粘度大于1600pa·s，随着剪切速率增加粘度迅速减少，剪切速率为100s-1时粘度小于10pa·s，屈服应力大于160pa，并有明显的触变环。
本领域的技术人员容易理解，以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (8)

1.一种用于立体光刻成型的触变性陶瓷膏体材料，其包括有以下组分，按照质量分数计为，陶瓷粉体70-80wt％；触变剂3-15wt％；光固化树脂10-25wt％；分散剂1-5wt％。
2.根据权利要求1所述的用于立体光刻成型的触变性陶瓷膏体材料，其特征在于，所述的陶瓷粉体为β-磷酸三钙、羟基磷灰石、生物玻璃、氧化铝、氧化镁和氧化锆中的一种或任意两种的混合。
3.根据权利要求1所述的用于立体光刻成型的触变性陶瓷膏体材料，其特征在于，所述的触变剂为气相二氧化硅、聚酰胺蜡、聚乙二醇、琼脂、蓖麻油衍生物、聚烯烃蜡、改性聚脲的N一甲基吡咯烷酮溶液中的一种或多种的混合。
4.根据权利要求1所述的用于立体光刻成型的触变性陶瓷膏体材料，其特征在于，所述的分散剂为磷酸酯、聚丙烯酸铵、聚丙烯酸酯中的一种或两种的混合。
5.根据权利要求1所述的用于立体光刻成型的触变性陶瓷膏体材料，其特征在于，所述的光固化树脂按质量分数由以下组分组成：98-99.5wt％的光固化树脂单体和0.5-2wt％的光引发剂。
6.根据权利要求5所述的用于立体光刻成型的触变性陶瓷膏体材料，其特征在于，所述的光固化树脂单体为丙烯酸月桂酯、三环癸基二甲醇二丙烯酸酯、丙氧基化新戊二醇二丙烯酸酯、烷氧基化季戊四醇四丙烯酸酯、乙氧基化三羟甲基三丙烯酸酯、聚乙二醇二丙烯酸酯、三丙二醇二丙烯酸酯、烷氧基化双酚A二(甲基)丙烯酸酯、甲氧基聚乙二醇(350)单丙烯酸酯、甲氧基丙氧基新戊二醇单丙烯酸酯、1，6-乙二醇二丙烯酸酯中的任意一种或多种的混合。
7.根据权利要求5所述的用于立体光刻成型的触变性陶瓷膏体材料，其特征在于，所述的光引发剂为2-羟基-2-甲基-苯基丙酮-1、1-羟基-环己基苯甲酮、2-羟基-2-甲基-对羟乙基醚基苯基丙酮-1、2,4,6-(三甲基苯甲酰基)二苯氧化膦中的任意一种或多种的混合。
8.权利要求1所述的用于立体光刻成型的触变性陶瓷膏体材料的制备方法，其特征在于，包括以下步骤：
a)光固化树脂预混液配置：将所需比例的光固化树脂单体、光引发剂、分散剂加入球磨罐中混合搅拌均匀得到预混液；
b)分步加入所需比例的陶瓷粉体，球磨使其均匀地分散在预混液中；
c)继续分步加入所需比例的触变剂，球磨得到符合流变性能要求膏体材料。
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