CN107098715A - 一种基于双重固化体系粘接剂的陶瓷零件3d打印方法 - Google Patents

一种基于双重固化体系粘接剂的陶瓷零件3d打印方法 Download PDF

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CN107098715A
CN107098715A CN201710284231.3A CN201710284231A CN107098715A CN 107098715 A CN107098715 A CN 107098715A CN 201710284231 A CN201710284231 A CN 201710284231A CN 107098715 A CN107098715 A CN 107098715A
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bonding agent
ceramic part
ceramic
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鲁中良
杨强
李涤尘
万伟舰
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Xian Jiaotong University
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Abstract

本发明公开了一种基于光固化粘接剂的陶瓷零件3D打印方法，第一重固化体系中，光敏树脂基的粘接剂在紫外光的照射下很快就会发生固化将粉末粘接成形，固化效率高，且该光敏树脂基粘接剂在见到紫外光才会固化，粘接剂在喷嘴中由于不会见到紫外光，因此不会发生固化堵塞打印喷嘴。第二重固化体系中，环氧树脂基粘接剂在固化触发剂聚硫醇的加入下也可以快速发生固化，且环氧树脂与聚硫醇触发剂是在不同的喷嘴中，由于双方不会接触，因此不会发生粘接剂的固化堵塞喷嘴；双重固化体系的粘接剂均为树脂基粘接剂，在配制过程中始终没有水的加入，因此可以用来粘接成型水溶性陶瓷粉末，同时双重固化体系成形的陶瓷零件素坯具有很高的强度和成形精度。

Description

一种基于双重固化体系粘接剂的陶瓷零件3D打印方法
技术领域
本发明属于增材制造领域，具体涉及一种基于双重固化体系粘接剂的陶瓷零件3D打印方法。
背景技术
陶瓷粉末3D打印(3DP)是一种新型的陶瓷零件成形方法，它具有“粘接剂喷射”和“粉床”两个特点，其主要是通过控制喷头选择性的喷射粘接剂粘接陶瓷粉末，形成一层截面薄层，待一层扫描喷射结束后，工作台下降一层厚度，重新铺上一层新的陶瓷粉末，继续选择性的喷射粘接剂，再形成一个截面薄层，同时薄层也将与已成形零件粘接在一起，从而实现逐层堆积成形零件。零件成形完毕后，再通过一些后处理工艺，如脱脂、致密化、高温强化烧结等，最终获得高强度致密化的陶瓷零件。
与其它具有“粉末床”的3D打印技术如选择性激光烧结和选择性激光熔化技术相比，粉末3D打印工艺主要是利用粘接剂而不是通过烧结或烧熔的方式将粉末粘结成形，因此粘接剂的特性是决定陶瓷零件成形特性的一个最重要的因素。在粉末3D打印工艺中，粘接剂的功用是将粉体胶合产生结合力使之成型。粘接剂通常要具有性能稳定、耐储存、对喷头无腐蚀性、低黏度以及适宜的表面张力等特性。粘接剂通常可以分为三大类：一、本身具有粘接作用的液体粘接剂，此类粘结剂可以制成墨水，采用喷头将其喷射至粉床特定区域，通过液体的润湿和粘接作用使粉末粘接成形，待粘接剂固化、干燥后即可得到成形的陶瓷零件素坯；二、双组份粘结剂，其中一个组分的粘结剂与粉体混合铺于粉床上，另外一个组分的触发剂置于喷头中，当喷头将墨水触发剂喷射到指定区域时，粉床上的粘结剂在触发剂的作用下发生固化反应，粘结基体陶瓷粉末，从而得到成型的陶瓷零件素坯；三、本身可以与粉末反应固化的粘接剂，此类粘接剂中通常会含有诱发粉末固化的成分，喷嘴将粘接剂喷射在粉末上，粘接剂中的诱发成分就会诱导粉末发生固化反应，实现粘接成形。
然而现有的陶瓷粉末粘接剂面临着几个亟待解决的问题：
一、目前陶瓷粉末粘接剂主要是单组分挥发型的粘接剂，挥发型粘接剂喷在粉末表面需要较长时间来进行干燥，待溶剂完全挥发才能发生固化粘接成形，成型效率低，同时粘接剂在干燥固化干燥过程中，由于所需时间较长会与非选区粉末发生相互渗透影响，降低了成形精度。其次，在打印过程中，挥发型粘接剂会在喷嘴处发生挥发，导致粘接剂固化堵塞喷嘴；
二、普通的粘接剂通常采用都含有水分，无法实现对具有水溶性的陶瓷粉末进行粘接成形，例如氧化钙、氧化镁、氮化铝等易发生水解的陶瓷粉末进行粘接成型；
三、普通的粘接剂，尤其是水基的粘接剂，其表面张力都较大，在陶瓷素坯固化干燥过程中会引起较大的变形收缩或者翘曲变形，从而影响到陶瓷零件的形状精度。
因此，发明一种性质稳定、固化效率高、干燥固化收缩变形小，同时能够实现对水溶性陶瓷粉末有效粘接的粘接剂对陶瓷材料3D打印方法具有很重要的价值与意义。
发明内容
本发明的目的在于克服上述不足，提供一种基于双重固化体系粘接剂的陶瓷零件3D打印方法，其固化效率高，成型坯体强度大，喷嘴不易堵塞，且干燥收缩小，成形精度高。
为了达到上述目的，本发明包括以下步骤：
步骤一，根据质量分数，将80％～90％的光敏树脂作为粘接剂基体材料，加入10％～20％的改性剂进行粘接剂的改性，添加0％～5％的光引发剂提高粘接剂的光固化速率，添加0％～5％的着色剂进行粘接剂的着色，构成第一重固化体系；
步骤二，采用80％～90％的环氧树脂作为粘接剂基体材料，加入10％～20％的改性剂进行粘接剂的改性，作为双组份固化的组分一，采用环氧树脂低温快速固化剂作为双组份固化的组分二，构成第二重固化体系；
步骤三，将需要成形的陶瓷材料粉末进行颗粒级配，并加入0％～5％质量分数的矿化剂和0％～5％质量分数的增强用短切纤维，并将其均匀混合；
步骤四，对待制造的陶瓷零件建立三维CAD模型，并建立分层和扫描路径的数据，导入陶瓷粉末3D打印设备；
步骤五，利用步骤一中的粘接剂和步骤二中制备的陶瓷粉末进行3D打印成形，打印完成后去除未粘接粉末，获得双重固化体系粘接剂粘接成形的陶瓷零件素坯；
步骤六，根据陶瓷材料组分，对陶瓷零件素坯脱脂和预烧结；
步骤七，对脱脂预烧结后的陶瓷零件坯体进行致密化处理；
步骤八，对致密化处理后的陶瓷零件再进行高温强化烧结，获得高强度致密陶瓷零件。
所述步骤一中，光敏树脂改性剂为甲醇或乙醇，着色剂为有机墨水；
所述步骤二中，环氧树脂改性剂为叔丁醇或乙二醇，低温快速固化剂为聚硫醇。
所述步骤三中，陶瓷粉末粒度为300目～1200目，增强用短切纤维的长度为0.5mm～2mm。
所述步骤三中，矿化剂为陶瓷材料所对应的烧结助剂。
所述步骤五中，打印过程中喷嘴在计算机的控制下按照所需路径喷射双重固化体系粘接剂将陶瓷粉末粘接成形，第一喷头中喷射的混合粘接剂中的光固化粘接剂在上方紫外光的照射下发生固化，同时第二喷头中喷射的低温快速固化剂与第一喷头中的环氧树脂固化剂再次发生固化，形成双重固化，最终成形为所需陶瓷零件素坯。
所述步骤六中，陶瓷素坯脱脂和预烧结工艺为大气脱脂预烧结或真空脱脂预烧结。
所述步骤七中，陶瓷坯体致密化处理工艺采用反应熔渗或化学气相沉积工艺。
所述步骤八中，高温强化烧结工艺采用热等静压烧结。
与现有技术相比，本发明具有以下有益效果：
1、第一重固化体系中，光敏树脂基的粘接剂在紫外光的照射下很快就会发生固化将粉末粘接成形，固化效率高，且该光敏树脂基粘接剂在见到紫外光才会固化，粘接剂在喷嘴中由于不会见到紫外光，因此不会发生固化堵塞打印喷嘴；
2、第二重固化体系中，环氧树脂基粘接剂在固化触发剂聚硫醇的加入下也可以快速发生固化，且环氧树脂与聚硫醇触发剂是在不同的喷嘴中，由于两组分不会产生接触，因此不会触发粘接剂的固化堵塞喷嘴；
3、双重固化体系的粘接剂均为树脂基粘接剂，在配制过程中始终没有水的加入，因此可以用来3D打印成形水溶性陶瓷粉末；
4、树脂基粘接剂固化后强度较高，且树脂的表面张力较小，在干燥固化过程中收缩变形小，不会出现严重的翘曲变形，提高了成型陶瓷零件的尺寸精度。
附图说明
图1为本发明的原理图；
图2为本发明的流程图；
图中，1、紫外光灯；2、紫外光；3、光敏树脂基和环氧树脂基混合粘接剂；4、铺粉辊；5、粉缸；6、第一喷嘴；7、第二喷嘴；8、聚硫醇触发剂；9、成型件；10、陶瓷粉末；11、升降台。
具体实施方式
下面结合附图和实施例对本发明做进一步说明。
实施例1
本发明提供的一种基于光固化粘接剂的Al2O3陶瓷零件3D打印方法，具体内容如下：
1)采用85％质量分数的光敏树脂作为粘接剂基体材料，加入10％质量分数的乙醇改性剂进行粘接剂的改性，添加3％质量分数的光引发剂提高粘接剂的光固化速率，添加2％质量分数的着色剂进行粘接剂的着色，配制出第一重固化体系的光敏树脂基粘接剂；
2)采用90％质量分数的环氧树脂作为粘接剂基体材料，加入10％质量分数的乙二醇改性剂进行粘接剂的改性，作为双组份固化的组分一，采用聚硫醇(环氧树脂低温快速固化剂)作为双组份固化的组分二，构成第二重固化体系；
3)将光敏树脂基粘接剂与改性后的环氧树脂粘接剂混合后，加入第一喷嘴中，将聚硫醇触发剂加入第二喷嘴中；
4)将40μm、20μm和5μm的Al2O3粉末按照50：35：15的质量比进行颗粒级配，再向级配后的陶瓷材料粉末加入5％质量分数的纳米SiO2和5％质量分数的短切Al2O3纤维，并将其均匀混合；
5)对待制造的陶瓷零件建立三维CAD模型，并建立分层和扫描路径的数据，导入陶瓷粉末3D打印设备；
6)利用步骤1)中的粘接剂和步骤2)中制备的陶瓷粉末进行3D打印成形，打印完成后去除未粘接的Al2O3粉末，获得双重固化粘接剂粘接成形的Al2O3陶瓷零件素坯；
7)对成型的Al2O3陶瓷零件素坯进行950℃大气脱脂预烧结；
8)对脱脂预烧结后的Al2O3陶瓷零件坯体进行浸渍两次硅溶胶处理；
9)对致密化处理后的Al2O3陶瓷零件在大气中进行1350℃高温强化烧结，获得高强度致密Al2O3陶瓷零件。
实施例2
本发明提供的一种基于光固化粘接剂的CaO-MgO复合陶瓷零件3D打印方法，具体内容如下：
1)采用85％质量分数的光敏树脂作为粘接剂基体材料，加入10％质量分数的乙醇改性剂进行粘接剂的改性，添加3％质量分数的光引发剂提高粘接剂的光固化速率，添加2％质量分数的着色剂进行粘接剂的着色，配制出第一重固化体系的光敏树脂基粘接剂；
2)采用90％质量分数的环氧树脂作为粘接剂基体材料，加入10％质量分数的乙二醇改性剂进行粘接剂的改性，作为双组份固化的组分一，采用聚硫醇(环氧树脂低温快速固化剂)作为双组份固化的组分二，构成第二重固化体系；
3)将光敏树脂基粘接剂与改性后的环氧树脂粘接剂混合后，加入第一喷嘴中，将聚硫醇触发剂加入第二喷嘴中；
4)将40μm、20μm的CaO粉末和5μm的MgO粉末按照50：35：15的质量比进行颗粒级配，再向级配后的陶瓷材料粉末加入5％质量分数的纳米ZrO2和5％质量分数的短切ZrO2纤维，并将其均匀混合；
5)对待制造的陶瓷零件建立三维CAD模型，并建立分层和扫描路径的数据，导入陶瓷粉末3D打印设备；
6)利用步骤1)中的粘接剂和步骤2)中制备的陶瓷粉末进行3D打印成形，打印完成后去除未粘接的CaO-MgO粉末，获得双重固化粘接剂粘接成形的CaO-MgO陶瓷零件素坯；
7)对成型的CaO-MgO陶瓷零件素坯进行1200℃脱脂预烧结；
8)对脱脂预烧结后的CaO-MgO陶瓷零件坯体进行熔渗反应渗镁；
9)对渗镁处理后的CaO-MgO陶瓷零件在真空中进行1550℃高温强化烧结，获得高强度致密CaO-MgO陶瓷零件。
实施例3
本发明提供的一种基于光固化粘接剂的SiC复合陶瓷零件3D打印方法，具体内容如下：
1)采用85％质量分数的光敏树脂作为粘接剂基体材料，加入10％质量分数的乙醇改性剂进行粘接剂的改性，添加3％质量分数的光引发剂提高粘接剂的光固化速率，添加2％质量分数的着色剂进行粘接剂的着色，配制出第一重固化体系的光敏树脂基粘接剂；
2)采用90％质量分数的环氧树脂作为粘接剂基体材料，加入10％质量分数的乙二醇改性剂进行粘接剂的改性，作为双组份固化的组分一，采用聚硫醇(环氧树脂低温快速固化剂)作为双组份固化的组分二，构成第二重固化体系；
3)将光敏树脂基粘接剂与改性后的环氧树脂粘接剂混合后，加入第一喷嘴中，将聚硫醇触发剂加入第二喷嘴中；
4)将40μm、20μm和5μm的SiC粉末按照50：35：15的质量比进行颗粒级配，再向级配后的陶瓷粉末5％质量分数的短切SiC纤维，并将其均匀混合；
5)对待制造的陶瓷零件建立三维CAD模型，并建立分层和扫描路径的数据，导入陶瓷粉末3D打印设备；
6)利用步骤1)中的粘接剂和步骤2)中制备的陶瓷粉末进行3D打印成形，打印完成后去除未粘接的SiC粉末，获得双重固化粘接剂粘接成形的陶瓷零件素坯；
7)对成型的SiC陶瓷零件素坯进行1000℃真空脱脂预烧结；
8)对脱脂预烧结后的SiC陶瓷零件坯体进行气相沉积致密化处理；
9)对气相沉积处理后的SiC陶瓷零件再进行1450℃热等静压高温强化烧结，获得高强度致密SiC陶瓷零件。

Claims (9)

1.一种基于双重固化体系粘接剂的陶瓷零件3D打印方法，其特征在于，包括以下步骤：
步骤一，根据质量分数，将80％～90％的光敏树脂作为粘接剂基体材料，加入10％～20％的改性剂进行粘接剂的改性，添加0％～5％的光引发剂提高粘接剂的光固化速率，添加0％～5％的着色剂进行粘接剂的着色；
步骤二，采用80％～90％的环氧树脂作为粘接剂基体材料，加入10％～20％的改性剂进行粘接剂的改性，作为双组份固化的组分一，采用环氧树脂低温快速固化剂作为双组份固化的组分二；
步骤三，将需要成形的陶瓷材料粉末进行颗粒级配，并加入0％～5％质量分数的矿化剂和0％～5％质量分数的增强用短切纤维，并将其均匀混合；
步骤四，对待制造的陶瓷零件建立三维CAD模型，并建立分层和扫描路径的数据，导入陶瓷粉末3D打印设备；
步骤五，利用步骤一中的粘接剂和步骤二中制备的陶瓷粉末进行3D打印成形，打印完成后去除未粘接粉末，获得光固化粘接剂粘接成形的陶瓷零件素坯；
步骤六，根据陶瓷材料组分，对陶瓷零件素坯脱脂和预烧结；
步骤七，对脱脂预烧结后的陶瓷零件坯体进行致密化处理；
步骤八，对致密化处理后的陶瓷零件再进行高温强化烧结，获得高强度致密陶瓷零件。
2.根据权利要求1所述的一种基于双重固化体系粘接剂的陶瓷零件3D打印方法，其特征在于，所述步骤一中，光敏树脂改性剂为甲醇或乙醇，着色剂为有机墨水。
3.根据权利要求1所述的一种基于双重固化体系粘接剂的陶瓷零件3D打印方法，其特征在于，所述步骤二中，环氧树脂改性剂为叔丁醇或乙二醇，低温快速固化剂为聚硫醇。
4.根据权利要求1所述的一种基于双重固化体系粘接剂的陶瓷零件3D打印方法，其特征在于，所述步骤三中，陶瓷粉末粒度为300目～1200目，增强用短切纤维的长度为0.5mm～2mm。
5.根据权利要求1所述的一种基于双重固化体系粘接剂的陶瓷零件3D打印方法，其特征在于，所述步骤三中，矿化剂为陶瓷材料所对应的烧结助剂。
6.根据权利要求1所述的一种基于双重固化体系粘接剂的陶瓷零件3D打印方法，其特征在于，所述步骤五中，打印过程中喷嘴在计算机的控制下按照所需路径喷射双重固化粘接剂将陶瓷粉末粘接成形，第一喷头中喷射的混合粘接剂中的光固化粘接剂在上方紫外光的照射下发生固化，同时第二喷头中喷射的低温快速固化剂与第一喷头中的环氧树脂固化剂再次发生固化，形成双重固化，最终成形为所需陶瓷零件素坯。
7.根据权利要求1所述的一种基于双重固化体系粘接剂的陶瓷零件3D打印方法，其特征在于，所述步骤六中，陶瓷素坯脱脂和预烧结工艺为大气脱脂预烧结或真空脱脂预烧结。
8.根据权利要求1所述的一种基于双重固化体系粘接剂的陶瓷零件3D打印方法，其特征在于，所述步骤七中，陶瓷坯体致密化处理工艺采用反应熔渗或化学气相沉积工艺。
9.根据权利要求1所述的一种基于双重固化体系粘接剂的陶瓷零件3D打印方法，其特征在于，所述步骤八中，高温强化烧结工艺采用热等静压烧结。
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CN111482602A (zh) * 2020-04-09 2020-08-04 北京科技大学 防堵塞喷头的基于光固化剂喷射的3d打印装置及方法
CN112961457A (zh) * 2020-05-11 2021-06-15 深圳市光韵达增材制造研究院 一种3d打印方法
CN113149650A (zh) * 2021-04-25 2021-07-23 陕西理工大学 一种基于sla的碳材料零件用光敏树脂及零件的制备方法
CN113459242A (zh) * 2021-09-01 2021-10-01 季华实验室 一种3d打印方法
CN114057490A (zh) * 2021-11-29 2022-02-18 宁波伏尔肯科技股份有限公司 一种用于制备大尺寸陶瓷的方法
CN114620998A (zh) * 2022-03-07 2022-06-14 西北工业大学 一种用于粉末3d打印高强度素坯的粘结剂组合物及打印方法
CN115431376A (zh) * 2022-08-16 2022-12-06 华中科技大学 高强度大型复杂陶瓷素坯及其三维喷印成形方法和装备
CN115286408A (zh) * 2022-08-17 2022-11-04 中国科学院上海硅酸盐研究所 一种基于颗粒级配复合技术的激光3d打印制备碳化硅复合材料部件的方法
CN115286408B (zh) * 2022-08-17 2023-03-10 中国科学院上海硅酸盐研究所 一种基于颗粒级配复合技术的激光3d打印制备碳化硅复合材料部件的方法
CN115635677A (zh) * 2022-10-28 2023-01-24 哈尔滨工业大学 一种快速固化双组分粘结剂喷射3d打印的方法

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