CN110002884B - 一种3d打印用陶瓷料浆及其制备方法和应用 - Google Patents
一种3d打印用陶瓷料浆及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一种3D打印用陶瓷料浆及其制备方法和应用,所述3D打印用陶瓷料浆包括陶瓷粉体、具有亲水基团的交联剂、惰性稀释剂、光引发剂和添加剂。交联剂均为水溶性丙烯酸酯,与陶瓷粉体折射率的差值较水体系的小,降低了料浆体系的散射,有利于打印高精度陶瓷部件。
Description
技术领域
本发明涉及陶瓷料浆,尤其涉及一种3D打印用陶瓷料浆及其制备方法和应用。
背景技术
目前文献报道的光固化3D打印用陶瓷料浆多采用亲油性树脂,如中国专利CN108083777 A中提到的树脂交联剂均为油性体系,油性体系再生产过程中会存在以下两方面的问题:
1、在料浆生产设备清洗过程中需要用大量的有机清洗剂(如无水乙醇等),在国家大力提倡绿色环保的发展理念下,亲油性树脂所生产的陶瓷料浆已不能适应生产需求;
2、在坯体的烧制时,坯体内部的树脂排出需要长时间的高温干燥处理,增加的制作成本,若干燥处理时间过短,交联树脂不能完全排出,坯体很容易出现裂纹,为坯体的烧制带来许多困难;
3、传统的油性树脂体系如HDDA、TPGDA、乙氧化/丙氧化丙烯酸树脂体系,制备的料浆中陶瓷固含量偏低,难以进一步提升固相含量,固化后素坯韧性较差,从打印平台取件时容易损伤素坯;并且剪切黏度高,烧结时坯体收缩较大,烧制难度较高导致成品率低。
发明内容
为了解决上述技术问题,本发明的目的在于提供一种3D打印用陶瓷料浆及其制备方法和应用。
根据本发明的一个方面,提供了一种3D打印用陶瓷料浆,包括:主体成分、添加剂;
所述主体成分包括陶瓷粉体、具有亲水基团的交联剂、惰性稀释剂;
所述添加剂包括光引发剂。
进一步的,所述主体成分中固液质量比为(1.5-9):1,其中,惰性稀释剂为交联剂质量的20-30%。
进一步的,所述光引发剂为交联剂质量的0.5-4%;
和/或
还包括分散剂,所述分散剂为陶瓷粉体质量的0.1-6%。
进一步的,所述具有亲水基团的交联剂包括交联组分A和交联组分B;
所述交联组分A为一种或多种具有亲水基团的丙烯酸酯,所述交联组分B为聚乙二醇二丙烯酸酯。
进一步的,所述交联组分A与交联组分B质量之比为1:1~14:1。
进一步的,所述交联组分A包括以下至少一种:丙烯酰吗啉、丙烯酸羟乙酯、甲基丙烯酸甲酯、4-羟基丁基丙烯酸酯。
进一步的,所述陶瓷粉体的粒径为50nm-5μm,比表面积小于50m2/g。
进一步的,所述光引发剂包括以下至少一种:2-羟基-2-甲基-1-苯基-1-丙酮、苯基双(2,4,6-三甲基苯甲酰基)氧化膦、2,4,6-三甲基苯甲酰基苯基膦酸乙酯。
和/或
所述惰性稀释剂包括以下至少一种:乙二醇、丙三醇、丁醇、丙二醇丁醚、异丙醇。
根据本发明的另一个方面,提供了一种3D打印用陶瓷料浆的制备方法,包括以下步骤:
S1:将具有亲水基团的交联剂与惰性稀释剂混合,其中,惰性稀释剂为交联剂质量的20-30%;
S2:加入分散剂,所述分散剂为陶瓷粉体质量的0.1-6%,陶瓷粉体质量按照固液质量比为(1.5-9):1计算;
S3:加入陶瓷粉体,研磨分散10-24小时;
S4:加入光引发剂,所述光引发剂为交联剂质量的0.5-4%,继续研磨分散1-5h,制得3D打印用陶瓷料浆。
根据本发明的另一个方面,提供了一种上述任一所述的3D打印用陶瓷料浆的应用,所述3D打印用陶瓷料浆用于成型精密部件。
与现有技术相比,本发明具有以下有益效果:
1、本发明采用的交联剂均为水溶性丙烯酸酯,本身对环境基本无污染,生产设备可以用水清洗,大大降低对环境的伤害,另外,制备陶瓷料浆所用的陶瓷粉体在大气环境中会吸附大气中的水汽,在陶瓷粉体表面产生吸附水,产生羟基基团,亲水树脂的亲水基团可以很好的与表面吸附水结构产生氢键,能够减少分散剂的使用量。
2、本发明料浆应用时,经过紫外光照射引发光固化反应,一是可以降低料浆体系粘度,若水性体系的料浆达到油性体系料浆的黏度,则可以提高料浆中陶瓷粉体的固相含量,增加坯体烧制后的致密性;二是惰性稀释剂分子本身不参与光固化反应,但可以在光固化反应时随陶瓷颗粒、交联剂一起原位固定到坯体中,由于惰性稀释剂的沸点小于交联剂,后续干燥处理过程排胶时小分子惰性稀释剂可以提前从素坯中挥发出来,可以打开坯体颗粒间的通道,有利于坯体的后续排胶,大幅降低排胶时间,降低烧制成本且坯体不易出现裂纹。
3、本发明3D打印用陶瓷料浆的制备方法,通过高速搅拌、球磨分散、除泡,陶瓷粉体质量按照固液质量比为(1.5-9):1,能够制备出40-60vol%的高固相含量、剪切黏度低的陶瓷料浆。
具体实施方式
为了更好的了解本发明的技术方案,下面结合具体实施例对本发明作进一步说明。
实施例1:
本实施例提供了一种3D打印用陶瓷料浆,包括:主体成分、添加剂;所述主体成分包括陶瓷粉体、具有亲水基团的交联剂、惰性稀释剂,所述添加剂包括光引发剂和分散剂;交联剂均为水溶性丙烯酸酯,本身对环境基本无污染,生产设备可以用水清洗,大大降低对环境的伤害。
所述主体成分中固液质量比为1.5:1,其中陶瓷粉体为固体、具有亲水基团的交联剂、惰性稀释剂为液体,其中,固液质量比为陶瓷粉体质量与具有亲水基团的交联剂、惰性稀释剂质量和之比。
所述陶瓷粉体的粒径为50nm,比表面积小于50m2/g,本实施例以微米级石英、氧化铝、氧化锆、氮化硅等粉体的一种或多种作为陶瓷粉体,其中,惰性稀释剂为交联剂质量的20%;所述具有亲水基团的交联剂包括交联组分A和交联组分B,降低料浆黏度,调节料浆的流变性,若同黏度油性体系料浆相比可以提高料浆中陶瓷粉体的固相含量,所述交联组分A为一种或多种具有亲水基团的丙烯酸酯(如丙烯酰吗啉或丙烯酸羟乙酯或甲基丙烯酸甲酯或4-羟基丁基丙烯酸酯等,丙烯酰吗啉ACMO折射率1.508,丙烯酸羟乙酯HEA折射率1.4469,甲基丙烯酸甲酯MMA折射率1.4142,羟基丁基丙烯酸酯4HBA 1.445),所述交联组分B为聚乙二醇二丙烯酸酯,包括以下至少一种:PEG200DMA、PEG400DMA、PEG600DMA,固化后素坯韧性较强,从打印平台取件时素坯不容易损伤。
具有亲水基团的丙烯酸酯与陶瓷粉体折射率的差值较水(水的折射率为1.33)体系的小,降低了料浆体系的散射,有利于打印高精度陶瓷部件。
所述光引发剂为交联剂质量的0.5%,所述分散剂为陶瓷粉体质量的0.1%,其中,所述光引发剂包括以下至少一种:2-羟基-2-甲基-1-苯基-1-丙酮、苯基双(2,4,6-三甲基苯甲酰基)氧化膦、2,4,6-三甲基苯甲酰基苯基膦酸乙酯;所述惰性稀释剂包括以下至少一种:乙二醇、丙三醇、丁醇、丙二醇丁醚、异丙醇。
本实施例制备陶瓷料浆所用的陶瓷粉体在大气环境中会吸附大气中的水汽,在陶瓷粉体表面产生吸附水,产生羟基基团,亲水树脂的亲水基团可以很好的与表面吸附水结构产生氢键,能够减少分散剂的使用量。
本实施例以微米级石英、氧化铝、氧化锆、氮化硅等粉体的一种或多种作为陶瓷粉体,能够制备出40-60vol%的高固相含量、剪切黏度低的陶瓷料浆,其中,石英料浆作为陶瓷粉体制得的料浆固体质量分数为59.5-79.1%;氧化铝作为陶瓷粉体制得的料浆中固体质量分数为72.7-85.7%;氧化锆作为陶瓷粉体制得的料浆中固体质量分数为80-90%,相比较油性体系料浆,可以提高料浆中陶瓷粉体的固相含量,增加坯体烧制后的致密性。
上述3D打印用陶瓷料浆的制备方法,包括以下步骤:
S1:将具有亲水基团的交联剂与惰性稀释剂混合,其中,惰性稀释剂为交联剂质量的20%;
S2:加入分散剂,所述分散剂为陶瓷粉体质量的0.1%,陶瓷粉体质量按照固液质量比为1.5:1计算;
S3:加入陶瓷粉体,研磨分散10小时;
S4:加入光引发剂,所述光引发剂为交联剂质量的0.5%,继续研磨分散1h,制得3D打印用陶瓷料浆,制备出陶瓷料浆固相含量40-60vol%、剪切黏度低,烧结时坯体收缩较小,成品率高。作为可选方案,本发明所涉及的水溶***联剂、惰性稀释剂、光引发剂和添加剂、3D打印用陶瓷料浆制备环境均为避光或黄光,以避免紫外线对原料及打印过程的影响。
本实施例提供一种可光固化的3D打印用陶瓷料浆的应用,用于成型精密部件,如导弹天线罩、泡沫结构陶瓷、人体植入物等。
实施例2:
本实施例提供了一种3D打印用陶瓷料浆,包括:主体成分、添加剂;所述主体成分包括陶瓷粉体、具有亲水基团的交联剂、惰性稀释剂,所述主体成分中固液质量比为9:1,所述陶瓷粉体的粒径为5μm,比表面积小于50m2/g。
其中,惰性稀释剂为交联剂质量的30%;所述具有亲水基团的交联剂包括交联组分A和交联组分B,所述交联组分A为一种或多种具有亲水基团的丙烯酸酯,所述交联组分B为聚乙二醇二丙烯酸酯,包括以下至少一种:PEG200DMA、PEG400DMA、PEG600DMA,所述交联组分A包括以下至少一种:丙烯酰吗啉、丙烯酸羟乙酯、甲基丙烯酸甲酯、4-羟基丁基丙烯酸酯。
所述添加剂包括光引发剂和分散剂,所述光引发剂为交联剂质量的4%,所述分散剂为陶瓷粉体质量的6%,其中,所述光引发剂包括以下至少一种:2-羟基-2-甲基-1-苯基-1-丙酮、苯基双(2,4,6-三甲基苯甲酰基)氧化膦、2,4,6-三甲基苯甲酰基苯基膦酸乙酯;所述惰性稀释剂包括以下至少一种:乙二醇、丙三醇、丁醇、丙二醇丁醚、异丙醇。
上述3D打印用陶瓷料浆的制备方法,包括以下步骤:
S1:将具有亲水基团的交联剂与惰性稀释剂混合,其中,惰性稀释剂为交联剂质量的30%;
S2:加入分散剂,所述分散剂为陶瓷粉体质量的6%,陶瓷粉体质量按照固液质量比为9:1计算;
S3:加入陶瓷粉体,研磨分散24小时;
S4:加入光引发剂,所述光引发剂为交联剂质量的4%,继续研磨分散5h,制得3D打印用陶瓷料浆。
本实施例提供一种3D打印用陶瓷料浆的应用,用于成型精密部件,如导弹天线罩、泡沫结构陶瓷、人体植入物等。
实施例3:
本实施例提供了一种3D打印用陶瓷料浆,包括:主体成分、添加剂;所述主体成分包括陶瓷粉体、具有亲水基团的交联剂、惰性稀释剂,所述主体成分中固液质量比为7:1,所述陶瓷粉体的粒径为3μm,比表面积小于50m2/g。
其中,惰性稀释剂为交联剂质量的25%;所述具有亲水基团的交联剂包括交联组分A和交联组分B,所述交联组分A为一种或多种具有亲水基团的丙烯酸酯,所述交联组分B为聚乙二醇二丙烯酸酯。所述交联组分A包括以下至少一种:丙烯酰吗啉、丙烯酸羟乙酯、甲基丙烯酸甲酯、4-羟基丁基丙烯酸酯。
所述添加剂包括光引发剂和分散剂,所述光引发剂为交联剂质量的2%,所述分散剂为陶瓷粉体质量的4%,其中,所述光引发剂包括以下至少一种:2-羟基-2-甲基-1-苯基-1-丙酮、苯基双(2,4,6-三甲基苯甲酰基)氧化膦、2,4,6-三甲基苯甲酰基苯基膦酸乙酯;所述惰性稀释剂包括以下至少一种:乙二醇、丙三醇、丁醇、丙二醇丁醚、异丙醇。
上述3D打印用陶瓷料浆的制备方法如下:
S1:将具有亲水基团的交联剂与惰性稀释剂混合,其中,惰性稀释剂为交联剂质量的30%;
S2:加入分散剂,所述分散剂为陶瓷粉体质量的4%,陶瓷粉体质量按照固液质量比为6:1计算;
S3:加入陶瓷粉体,研磨分散15小时;
S4:加入光引发剂,所述光引发剂为交联剂质量的2%,继续研磨分散3h,制得3D打印用陶瓷料浆。
本实施例提供一种3D打印用陶瓷料浆的应用,用于成型精密部件,如导弹天线罩、泡沫结构陶瓷、人体植入物等。
实施例4:
本实施例提供了一种3D打印用陶瓷料浆,包括:主体成分、添加剂;所述主体成分包括陶瓷粉体、具有亲水基团的交联剂、惰性稀释剂,所述主体成分中固液质量比为5.5:1,所述陶瓷粉体的粒径为3μm,比表面积小于50m2/g。
其中,惰性稀释剂为交联剂质量的8%;所述具有亲水基团的交联剂包括交联组分A和交联组分B,所述交联组分A为一种或多种具有亲水基团的丙烯酸酯,所述交联组分B为聚乙二醇二丙烯酸酯,包括以下至少一种:PEG200DMA、PEG400DMA、PEG600DMA,所述交联组分A包括以下至少一种:丙烯酰吗啉、丙烯酸羟乙酯、甲基丙烯酸甲酯、4-羟基丁基丙烯酸酯。
所述添加剂包括光引发剂和分散剂,所述光引发剂为交联剂质量的3.1%,所述分散剂为陶瓷粉体质量的3%,其中,所述光引发剂包括以下至少一种:2-羟基-2-甲基-1-苯基-1-丙酮、苯基双(2,4,6-三甲基苯甲酰基)氧化膦、2,4,6-三甲基苯甲酰基苯基膦酸乙酯;所述惰性稀释剂包括以下至少一种:乙二醇、丙三醇、丁醇、丙二醇丁醚、异丙醇。
上述3D打印用陶瓷料浆的制备方法如下:
S1:将具有亲水基团的交联剂与惰性稀释剂混合,其中,惰性稀释剂为交联剂质量的28%;
S2:加入分散剂,所述分散剂为陶瓷粉体质量的3%,陶瓷粉体质量按照固液质量比为5.5:1计算;
S3:加入陶瓷粉体,混合球磨分散20小时;
S4:加入光引发剂,所述光引发剂为交联剂质量的3.1%,继续球磨分散4h,制得3D打印用陶瓷料浆。
本实施例提供一种3D打印用陶瓷料浆的应用,用于成型精密部件,如导弹天线罩、泡沫结构陶瓷、人体植入物等。
以上描述仅为本申请的较佳实施例以及对所运用技术原理的说明。本领域技术人员应当理解,本申请中所涉及的发明范围,并不限于上述技术特征的特定组合而成的技术方案,同时也应涵盖在不脱离所述发明构思的情况下,由上述技术特征或其等同特征进行任意组合而形成的其它技术方案。例如上述特征与本申请中公开的(但不限于)具有类似功能的技术特征进行互相替换而形成的技术方案。
Claims (8)
1.一种3D打印用陶瓷料浆,其特征在于,包括:主体成分、添加剂;
所述主体成分包括陶瓷粉体、具有亲水基团的交联剂、惰性稀释剂,所述主体成分中固液质量比为(5.5-9):1;
其中,所述具有亲水基团的交联剂包括交联组分A和交联组分B,所述交联组分A为一种或多种具有亲水基团的丙烯酸酯,所述交联组分B为聚乙二醇二丙烯酸酯;
所述惰性稀释剂包括以下至少一种:乙二醇、丙三醇、丁醇、丙二醇丁醚、异丙醇,惰性稀释剂为交联剂质量的20-30%,所述惰性稀释剂的沸点小于交联剂;
所述添加剂包括分散剂、光引发剂,所述分散剂为陶瓷粉体质量的0.1%。
2.如权利要求1所述的3D打印用陶瓷料浆,其特征在于,所述光引发剂为交联剂质量的0.5-4%。
3.如权利要求1所述的3D打印用陶瓷料浆,其特征在于,所述交联组分A与交联组分B质量之比为1:1~14:1。
4.如权利要求1所述的3D打印用陶瓷料浆,其特征在于,所述交联组分A包括以下至少一种:丙烯酰吗啉、丙烯酸羟乙酯、4-羟基丁基丙烯酸酯。
5.如权利要求1所述的3D打印用陶瓷料浆,其特征在于,所述陶瓷粉体的粒径为50nm-5μm,比表面积小于50m2/g。
6.如权利要求1所述的3D打印用陶瓷料浆,其特征在于,所述光引发剂包括以下至少一种:2-羟基-2-甲基-1-苯基-1-丙酮、苯基双(2,4,6-三甲基苯甲酰基)氧化膦、2,4,6-三甲基苯甲酰基苯基膦酸乙酯。
7.一种权利要求1-6任意一项所述的3D打印用陶瓷料浆的制备方法,其特征在于,包括以下步骤:
S1:将具有亲水基团的交联剂与惰性稀释剂混合,其中,惰性稀释剂为交联剂质量的20-30%;
S2:加入分散剂,所述分散剂为陶瓷粉体质量的0.1%,
S3:加入陶瓷粉体,研磨分散10-24小时,其中,陶瓷粉体质量按照固液质量比为(5.5-9):1计算 ;
S4:加入光引发剂,所述光引发剂为交联剂质量的0.5-4%,继续研磨分散1-5h,制得3D打印用陶瓷料浆。
8.一种权利要求1-6任一所述的3D打印用陶瓷料浆的应用,其特征在于:所述3D打印用陶瓷料浆用于成型精密部件。
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