CN108585799B - 一种新型陶瓷3d打印成型方法 - Google Patents

一种新型陶瓷3d打印成型方法 Download PDF

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CN108585799B
CN108585799B CN201810447784.0A CN201810447784A CN108585799B CN 108585799 B CN108585799 B CN 108585799B CN 201810447784 A CN201810447784 A CN 201810447784A CN 108585799 B CN108585799 B CN 108585799B
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郭伟明
吴利翔
牛文彬
魏世宏
尹梓绅
林华泰
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Guangdong University of Technology
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Abstract

本发明公开了一种新型陶瓷3D打印成型方法，其包括以下步骤：将陶瓷的3D结构模型输入至3D打印机中；在3D打印机中设置两个料槽，分别为装有光敏树脂的料槽A和装有陶瓷浆料的料槽B；启动3D打印机开始打印，通过3D打印机控制料槽A利用光敏树脂打印陶瓷胚体的首层和/或支撑结构，通过3D打印机控制料槽B利用陶瓷浆料打印陶瓷胚体，直至得到陶瓷胚体；对陶瓷胚体进行脱脂和烧结得到陶瓷产品。本发明通过设计陶瓷3D打印机的系统和料槽，采用光敏树脂打印陶瓷的首层以及支撑结构，解决了陶瓷浆料打印过程中首层成型难的问题，并且，由于光敏树脂可以直接在脱脂过程中去除，因此，可以实现在打印坯体时不用去除支撑，直接制备复杂形状陶瓷材料。

Description

一种新型陶瓷3D打印成型方法
技术领域
本发明涉及3D打印技术领域，具体涉及了一种新型陶瓷3D打印成型方法。
背景技术
3D打印制造技术是指基于离散材料逐层堆积成形的原理，通过CAD设计数据采用材料逐层累加的方法制造实体零件的技术。相对于传统的材料去除(切削加工)技术，是一种“自上而下”材料累加的制造方法。3D打印制造技术，解决许多过去难以制造的复杂结构零件的成形，并大大减少了加工工序，缩短了加工周期。而且越是复杂结构的产品，其制造的速度作用越显著。
陶瓷3D打印基于数字化直接成型，可实现各种复杂形状陶瓷材料的制备。目前，应用较广的陶瓷3D打印主要是光固化成型技术(SLA)，也称作数字光处理技术(DLP)。DLP技术打印陶瓷主要有两种途径，即陶瓷固溶于光敏树脂制备陶瓷浆料进行打印成型，另一种为制备陶瓷前驱体溶液进行打印。陶瓷浆料既可以打印氧化物，也可以打印非氧化物，并且具有更小的收缩率。因此，采用陶瓷浆料进行3D打印制备陶瓷材料作为DLP技术的主流。DLP技术通过对固含陶瓷颗粒的光敏树脂进行固化，进行逐层打印。
采用DLP技术对陶瓷浆料进行打印时，固含的陶瓷颗粒对陶瓷浆料的固化成型有影响，尤其对于自下往上打印原理的DLP技术，第一层很难在成型托盘上固化成型，然而，第一层的成型程度却对整体结构的打印成型起到关键作用。并且，采用DLP技术的打印成型过程中物体往往需要设计有支撑结构，复杂的支撑结构增加后续支撑结构去除工序的工作量，导致成本升高，效率低下。
发明内容
本发明目的在于克服现有技术的缺点与不足，提供了一种新型陶瓷3D打印成型方法，解决了陶瓷浆料打印过程中首层成型难的问题，优化了陶瓷3D打印的支撑结构设计，实现了不用去支撑制备复杂形状陶瓷材料的3D打印。
为实现上述目的，本发明采用的技术方案如下：
一种新型陶瓷3D打印成型方法，包括以下步骤：
将陶瓷的3D结构模型输入至3D打印机中；
在3D打印机中设置两个料槽，分别为装有光敏树脂的料槽A和装有陶瓷浆料的料槽B；
启动3D打印机开始打印，通过3D打印机控制料槽A利用光敏树脂打印陶瓷胚体的首层和/或支撑结构，通过3D打印机控制料槽B利用陶瓷浆料打印陶瓷胚体，直至得到陶瓷胚体；
对陶瓷胚体进行脱脂和烧结得到陶瓷产品。
本发明通过设计陶瓷3D打印机的系统和料槽，采用光敏树脂打印陶瓷的首层以及支撑结构，解决了陶瓷浆料打印过程中首层成型难的问题，并且，由于光敏树脂可以直接在脱脂过程中去除，因此，可以实现在打印坯体时不用去除支撑，直接制备复杂形状陶瓷材料。
作为本发明一种改进，所述步骤“启动3D打印机开始打印，通过3D打印机控制料槽A利用光敏树脂打印陶瓷胚体的首层和/或支撑结构，通过3D打印机控制料槽B利用陶瓷浆料打印陶瓷胚体，直至得到陶瓷胚体”具体过程为：所述支撑结构设置在陶瓷胚体的下方，先通过3D打印机控制料槽A利用光敏树脂打印陶瓷胚体的首层和支撑结构，再控制料槽B利用陶瓷浆料打印陶瓷胚体。
进一步地，所述料槽A盛装的光敏树脂是由10～90wt％单体、10～90wt％低聚物、0.1～5wt％光引发剂、0.1～5wt％光敏剂、0.1～5wt％增感剂和0.1～5wt％消泡剂组成。
作为本发明一种改进，所述料槽B盛装的陶瓷浆料是由分散剂改性的陶瓷粉体与光敏树脂混合再除泡处理后获得。
进一步地，所述的陶瓷浆料中陶瓷比例为30％～70％。
进一步地，所述的脱脂工艺为在3000～800℃下保温0.5～24h。
进一步地，所述的烧结工艺为在900～2200℃下保温0.5～24h。
与现有技术相比，本发明技术方案的创新点和有益效果在于：
本发明通过设计陶瓷3D打印机的系统和料槽，采用光敏树脂打印陶瓷的首层以及支撑结构，解决了陶瓷浆料打印过程中首层成型难的问题，并且，由于光敏树脂可以直接在脱脂过程中去除，因此，可以实现在打印坯体时不用去除支撑，直接制备复杂形状陶瓷材料。
附图说明
图1为本发明新型陶瓷3D打印成型方法的流程图；
图2为利用本发明方法打印得到的陶瓷产品图。
具体实施方式
下面结合附图和实施例对本发明作进一步说明。可以理解的是，此处所描述的具体实施例仅仅用于解释本发明，而非对本发明的限定。另外还需要说明的是，为了便于描述，附图中仅示出了与本发明相关的部分而非全部内容。
实施例1
请参考图1，一种新型陶瓷3D打印成型方法，包括以下步骤：
S1.将陶瓷的3D结构模型输入至3D打印机中。
S2.在3D打印机中设置两个料槽，分别为装有光敏树脂的料槽A和装有陶瓷浆料的料槽B；其中所述料槽A盛装的光敏树脂是由10～90wt％单体、10～90wt％低聚物、0.1～5wt％光引发剂、0.1～5wt％光敏剂、0.1～5wt％增感剂和0.1～5wt％消泡剂组成；所述料槽B盛装的陶瓷浆料是由分散剂改性的陶瓷粉体与光敏树脂混合再除泡处理后获得，所述的陶瓷浆料中陶瓷比例为30％～70％。
S3.启动3D打印机开始打印，通过3D打印机控制料槽A利用光敏树脂打印陶瓷胚体的首层和/或支撑结构，通过3D打印机控制料槽B利用陶瓷浆料打印陶瓷胚体，直至得到陶瓷胚体；
具体地，所述支撑结构设置在陶瓷胚体的下方，先通过3D打印机控制料槽A利用光敏树脂打印陶瓷胚体的首层和支撑结构，再控制料槽B利用陶瓷浆料打印陶瓷胚体。
S4.对陶瓷胚体进行脱脂和烧结得到陶瓷产品；
具体地，所述的脱脂工艺为在3000～800℃下保温0.5～24h；所述的烧结工艺为在900～2200℃下保温0.5～24h。
请参考图2，图2所示的为利用本发明方法打印得到的陶瓷产品，该陶瓷产品的首层和支撑结构采用光敏树脂打印而成，再在首层和支撑结构基础上继续打印出陶瓷胚体，解决了陶瓷浆料打印过程中首层成型难的问题。
本发明通过设计陶瓷3D打印机的系统和料槽，采用光敏树脂打印陶瓷的首层以及支撑结构，解决了陶瓷浆料打印过程中首层成型难的问题，并且，由于光敏树脂可以直接在脱脂过程中去除，因此，可以实现在打印坯体时不用去除支撑，直接制备复杂形状陶瓷材料。
具体地，在本实施例中，料槽A盛装的光敏树脂是由20％已二醇二丙烯酸酯单体，78％丙烯酸酯低聚物，0.5％(2,4,6-三甲基苯甲酰基)二苯基氧化膦光引发剂，0.5％苯并卟啉衍生物单酸光敏剂，0.5％脂肪族叔胺增感剂和0.5％巴斯夫-8034A消泡剂组成。料槽B盛装的陶瓷浆料是由0.1％油酸分散剂改性的陶瓷粉体与光敏树脂混合再进行0.5h除泡处理后获得。陶瓷固含量为50％，陶瓷粉体为Al2O3，纯度为99％，粒径为3μm。通过制备得到的Al2O3陶瓷致密度为98％，硬度为18GPa，抗弯强度为800MPa，断裂韧性为7MPa·m12。
实施例2
陶瓷粉体为ZrO2，纯度为99％，粒径为50nm；Al2O3粉体纯度99％，粒径为3μm。ZrO2：Al2O3的比例为10％：90％，陶瓷浆料中陶瓷比例为60％。按照实施例1方法制备得到ZTA陶瓷，其中脱脂和烧结工艺为：在650℃真空脱脂和1400℃烧结。本实施例制备得到ZTA陶瓷相对密度达到99％，硬度为17GPa，抗弯强度为1100Mpa，断裂韧性为10MPa·m12。
实施例3
陶瓷粉体Si3N4，纯度为99％，粒径为0.2μm；MgO粉体纯度99％，粒径为100nm；Y2O3粉体纯度99％，粒径为0.1μm。Si3N4：MgO：Y2O3的比例为93％：2％：5％，陶瓷浆料中陶瓷比例为50％。按照实施例1方法制备得到Si3N4陶瓷，其中脱脂和烧结工艺为：在700℃真空脱脂，在5MPa的氮气压力下进行1850℃气压烧结。本实施例制备得到Si3N4陶瓷相对密度达到99％，硬度为18GPa，抗弯强度为1000Mpa，断裂韧性为10MPa·m12。
实施例4
陶瓷粉体为ZrB2，纯度为99％，粒径为0.1μm；SiC粉体纯度为99％，粒径为30nm。ZrB2：SiC的比例为90％：10％，陶瓷浆料中陶瓷比例为40％。按照实施例1方法制备得到ZrB2-SiC陶瓷，其中脱脂和烧结工艺为：在650℃真空脱脂，在Ar保护气氛下进行2000℃烧结。本实施例制备得到ZrB2-SiC陶瓷相对密度达到99％，硬度为25GPa，抗弯强度为1000Mpa，断裂韧性为8MPa·m12。
实施例5
陶瓷粉体为SiC，纯度为99％，粒径为0.1μm，陶瓷浆料中陶瓷比例为50％。按照实施例1方法制备得到SiC陶瓷，其中脱脂和烧结工艺为：在650℃真空脱脂，在Ar保护气氛下进行1900℃烧结。本实施例制备得到SiC陶瓷相对密度达到99％，表层硬度为20GPa，抗弯强度为1100Mpa，断裂韧性为10MPa·m12。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (5)

1.一种新型陶瓷3D打印成型方法，其特征在于包括以下步骤：
将陶瓷的3D结构模型输入至3D打印机中；
在3D打印机中设置两个料槽，分别为装有光敏树脂的料槽A和装有陶瓷浆料的料槽B；所述料槽A盛装的光敏树脂是由10～90wt%单体、10～90wt%低聚物、0.1～5wt%光引发剂、0.1～5wt%光敏剂、0.1～5wt%增感剂和0.1～5wt%消泡剂组成；
启动3D打印机开始打印，通过3D打印机控制料槽A利用光敏树脂打印陶瓷胚体的首层和支撑结构，通过3D打印机控制料槽B利用陶瓷浆料打印陶瓷胚体，直至得到陶瓷胚体；前述步骤的具体过程为：所述支撑结构设置在陶瓷胚体的下方，先通过3D打印机控制料槽A利用光敏树脂打印陶瓷胚体的首层和支撑结构，再控制料槽B利用陶瓷浆料打印陶瓷胚体；对陶瓷胚体进行脱脂和烧结得到陶瓷产品。
2.根据权利要求1所述的新型陶瓷3D打印成型方法，其特征在于：所述料槽B盛装的陶瓷浆料是由分散剂改性的陶瓷粉体与光敏树脂混合再除泡处理后获得。
3.根据权利要求2所述的新型陶瓷3D打印成型方法，其特征在于：所述的陶瓷浆料中陶瓷比例为30%～70%。
4.根据权利要求1所述的新型陶瓷3D打印成型方法，其特征在于：所述的脱脂工艺为在3000～800℃下保温0.5～24h。
5.根据权利要求1所述的新型陶瓷3D打印成型方法，其特征在于：所述的烧结工艺为在900～2200℃下保温0.5～24h。
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