CN111943688B - 一种3d冷冻打印方法 - Google Patents

一种3d冷冻打印方法 Download PDF

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CN111943688B
CN111943688B CN202010851579.8A CN202010851579A CN111943688B CN 111943688 B CN111943688 B CN 111943688B CN 202010851579 A CN202010851579 A CN 202010851579A CN 111943688 B CN111943688 B CN 111943688B
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孙志强
张剑
王华栋
韩耀
吕毅
张昊
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Aerospace Research Institute of Materials and Processing Technology
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Abstract

本发明涉及一种3D冷冻打印方法。所述方法包括：调控打印空间温度的步骤：将打印空间的温度降低至‑40℃至‑80℃；设定打印参数的步骤：设置浆料挤出速率和打印单层高度；设置挤出头移动速率；挤出打印的步骤：将泥料挤出，使泥料一层层地粘接在打印底板上；层间结合与冷冻固化的步骤：层层泥料自动完成层间结合和冷冻固化。本发明通过对打印空间温度进行特定调控，对浆料挤出速率和打印单层高度进行特定设置后，使得3D打印装置挤出的泥料层层粘接在打印底板上时可以自动完成高强度的层间结合与冷冻固化，并且可以获得高强度生坯，使生坯可以在烧结前进行打磨等表面处理。

Description

一种3D冷冻打印方法
技术领域
本发明涉及增材制造技术领域，涉及一种3D冷冻打印方法。
背景技术
陶瓷构件具有优良力学性能、高的抗弯强度、优良的抗氧化性、良好的耐腐蚀性、高的抗磨损性以及低的摩擦系数，在航空航天领域应用广泛。
3D打印成型技术是近年来快速发展的一种新型成型工艺，结合后续烧结工艺大幅缩短了陶瓷构件的成型周期，解决了传统工艺无法克服的设计尺寸改变或者调整，将需要重新设计并制造模具；而制造模具成本较高、周期较长，制得的制品形状简单等一系列问题。
发明内容
(一)要解决的技术问题
3D冷冻打印的关键是如何通过冷冻固化实现层间的高强度结合，目前对于浆料的打印环境温度、挤出速率以及层间结合的时间对层间结合影响的研究较少，打印工艺及参数设定都有待研究。冷冻过程如何使得层间克服冰晶膨胀应力，实现高强度层间结合，是本专利发明关注的问题。
(二)技术方案
为了解决上述技术问题，本发明提供了如下技术方案：
一种3D冷冻打印方法，所述方法包括：
调控打印空间温度的步骤：将打印空间的温度降低至-40℃至-80℃；
设定打印参数的步骤：设置浆料挤出速率和打印单层高度；设置挤出头移动速率；
挤出打印的步骤：将泥料挤出，使泥料一层层地粘接在打印底板上；
层间结合与冷冻固化的步骤：层层泥料自动完成层间结合和冷冻固化。
2、根据技术方案1所述的方法，
通过控制打印空间冷气吹进量对打印空间的温度进行调控。
3、根据技术方案2所述的方法，
所述冷气为液氮汽化后的低温氮气。
4、根据技术方案1至3任一项所述的方法，
设置浆料挤出速率为0.5cm/s至2cm/s；和/或
设置打印层高为0.4mm至1mm。
5、根据技术方案1至4任一项所述的方法，
所述泥料包含陶瓷粉体和混合溶剂；
所述陶瓷粉体选自氧化硅、氧化铝、氧化锆、氮化硅、氮化铝中的任一种或多种；
所述混合溶剂为水。
6、根据技术方案5所述的方法，
所述泥料还包含助剂；
所述助剂为硅溶胶、聚乙二醇、聚乙烯醇中的任一种或多种。
7、根据技术方案1至6任一项所述的方法，
泥料的挤出厚度为0.3-1mm。
8、根据技术方案1至7任一项所述的方法，
泥料通过层间结合和冷冻固化后形成生坯，所述生坯的强度为300KPa。
9、根据技术方案8所述的方法，
所述方法还包括：
冷冻干燥的步骤：将生坯冷冻干燥；
烧结的步骤：将冷冻干燥后的生坯烧结。
10、根据技术方案9所述的方法，
在烧结前，对冷冻干燥后的生坯进行表面处理；
优选地，所述表面处理为打磨。
(三)有益效果
本发明的上述技术方案具有如下优点：
本发明通过对打印空间温度进行特定调控，对浆料挤出速率、打印单层高度以及挤出头移动速率进行特定设置后，使得3D打印装置挤出的泥料层层粘接在打印底板上时可以自动完成高强度的层间结合与冷冻固化，并且可以获得高强度生坯，使生坯可以在烧结前进行打磨等表面处理。
本发明提供的3D打印方法可以用来制造复杂陶瓷构件，如航空航天领域用陶瓷构件。
附图说明
图1是本发明提供的方法的流程示意图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面将结合本发明实施例，对本发明的技术方案进行清楚、完整地描述。显然，所描述的实施例是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明提供了一种3D冷冻打印方法，用于3D打印陶瓷构件。参考图1，本发明提供的这一3D冷冻打印方法包括：
调控打印空间温度的步骤：将打印空间的温度降低至-40℃至-80℃，例如，-40℃，-50℃，-60℃，-70℃，-80℃；该温度范围较为适宜，使得从打印空腔挤出的泥料层不是一挤出就固化，而是经过一段时间后才会由水结为冰实现冷冻固化，在这一段时间内，泥料层会与上一层泥料层融合，从而保证了打印材料的结合强度。在一些优选的实施方式中，通过控制打印空间冷气吹进量对打印空间的温度进行调控，所述冷气为液氮汽化后的低温氮气。需要说明的是，低温氮气指的是可以将打印空间温度降低至-40℃至-80℃的氮气。总的来说，通过控制打印空间低温氮气的吹进量对打印空间的温度进行调控，使打印空间的温度降低至零下40摄氏度至零下80摄氏度。
设定打印参数的步骤：设置浆料挤出速率和打印单层高度；设置挤出头移动速率。发明人在研究中发现，浆料挤出速率、打印单层高度以及设置出头移动速率影响泥料的层间结合速度。基于这一发现，在优选的实施方式中，通过调控打印空间温度至零下40摄氏度至零下80摄氏度，并设置浆料挤出速率为0.5cm/s至2cm/s(例如，0.5cm/s，1cm/s，1.5cm/s，2cm/s)，设置打印层高为0.4mm-1mm(例如，0.4mm，0.5mm，0.6mm，0.7mm，0.8mm，0.9mm，1mm)，设置挤出头移动速率为0.3cm/s至1.5cm/s(例如，0.3cm/s，0.4cm/s，0.5cm/s，1cm/s，1.5cm/s)，可以确保上下两层完成挤压融合的时间间隙为15-40s。
挤出打印的步骤：将泥料挤出，使泥料一层层地粘接在打印底板上。在该步骤中，本发明优选控制泥料的挤出厚度为0.3-1mm，例如，0.3mm，0.4mm，0.5mm，0.6mm，0.7mm，0.8mm，0.9mm，1mm。
对于泥料，所述泥料包含陶瓷粉体和混合溶剂，所述陶瓷粉体选自氧化硅、氧化铝、氧化锆、氮化硅、氮化铝中的任一种或多种，所述混合溶剂为水。所述泥料还可以包含助剂，所述助剂为硅溶胶、聚乙二醇、聚乙烯醇中的任一种或多种。本发明在制备水基浆料时使用的硅溶胶能够发生胶凝反应，生成Si-O-Si键，可进一步提升层间结合强度；聚乙二醇和聚乙烯醇的加入能够提高浆料的塑性，克服浆料泌水，确保浆料在挤出打印过程中保持稳定。需要说明的是，泥料中各组分的含量可以参考现有技术，本发明在此不再详述。
层间结合与冷冻固化的步骤：层层泥料自动完成层间结合和冷冻固化。经过对打印空间温度进行特定调控，对浆料挤出速率和打印单层高度进行特定设置后，通过3D打印装置挤出的泥料层层粘接在打印底板上时可以自动完成层间结合与冷冻固化，如，每当挤出一层泥料，新挤出的泥料层在一定应力下可与上一层泥料层融合在一起，完成层间的融合。新挤出的第二层泥料在一定应力下与第一层泥料融合在一起，完成层间的融合。当打印3-6层后，第一层与第二层泥料及其层间自动实现冷冻固化，后续其它层也自动实现冷冻固化。另外。在上述条件下3D打印得到的生坯(层间结合与冷冻固化后的材料即为生坯)强度可以达到300KPa以上，使生坯可以在烧结前进行打磨等表面处理。
冷冻干燥的步骤：将生坯冷冻干燥。冷冻干燥的工艺条件可参考现有技术，本发明在此不再详述。
烧结的步骤：将冷冻干燥后的生坯烧结，得到陶瓷构件。烧结的工艺科参考现有技术，本发明在此不再详述。
利用本发明提供的3D打印方法可以用来制造复杂陶瓷构件，如航空航天领域用陶瓷构件。
以下是本发明列举的实施例。
实施例1
控制打印空间低温氮气吹进量，使得打印空间的气温降低至-40℃。设置浆料挤出速率为0.5cm/s，设置打印层高为0.4mm，设置挤出头移动速率为0.3cm/s，确保上下两层完成挤压融合的时间间隙在15-40s。随后，通过电机将配制的氧化硅泥料(将粒径级配为小于200nm的粉体占4％，200nm-1.0μm的粉体占10％，1-10μm的粉体占40％，10-30μm的粉体占30％，大于30μm的粉体占16％的氧化硅陶瓷粉体分散到固含量为25％硅溶胶中，添加0.5％聚乙二醇和1％聚乙烯醇后，球磨8h，获得固含量70％的泥料，泥料的混合溶剂为水)挤出喷嘴，泥料的挤出厚度为0.3mm，泥料一层层地粘接在打印底板上；最后，完成层间结合与冷冻固化，新挤出的泥料层在一定应力下与上一层泥料层融合在一起，完成层间的融合。当打印4层后，第一层与第二层泥料及其层间实现冷冻固化，后续其它层也自动实现冷冻固化，最终得到生坯，生坯强度不低于300KPa。
将生坯进行冷冻干燥和烧结，得到陶瓷构件。
实施例2
控制打印空间低温氮气吹进量，使得打印空间的气温降低至-80℃。设置浆料挤出速率为1.5cm/s，设置打印层高为0.6mm，设置挤出头移动速率为1cm/s，确保上下两层完成挤压融合的时间间隙在15-40s。随后，通过电机将配制的氧化铝泥料(将粒径级配为小于200nm的粉体占3％，200nm-1.0μm的粉体占10％，1-10μm的粉体占40％，10-30μm的粉体占30％，大于30μm的粉体占17％的氧化硅陶瓷粉体分散到固含量为25％硅溶胶中，添加0.5％聚乙二醇和1％聚乙烯醇后，球磨8h，获得固含量65％的泥料，泥料的混合溶剂为水)挤出喷嘴，泥料的挤出厚度为0.5mm，泥料一层层地粘接在打印底板上；最后，完成层间结合与冷冻固化，新挤出的泥料层在一定应力下与上一层泥料层融合在一起，完成层间的融合。当打印6层后，第一层与第二层泥料及其层间实现冷冻固化，后续其它层也自动实现冷冻固化，最终得到生坯，生坯强度不低于300KPa。
将生坯进行冷冻干燥和烧结，得到陶瓷构件。
实施例3
控制打印空间低温氮气吹进量，使得打印空间的气温降低至-60℃。设置浆料挤出速率为2cm/s，设置打印层高为1mm，设置挤出头移动速率为1.5cm/s，确保上下两层完成挤压融合的时间间隙在15-40s。随后，通过电机将配制的氮化硅泥料(将粒径级配为小于200nm的粉体占4％，200nm-1.0μm的粉体占10％，1-10μm的粉体占40％，10-30μm的粉体占30％，大于30μm的粉体占16％的氧化硅陶瓷粉体分散到固含量为25％硅溶胶中，添加0.5％聚乙二醇和1％聚乙烯醇后，球磨8h，获得固含量70％的泥料，泥料的混合溶剂为水)挤出喷嘴，泥料的挤出厚度为1mm，泥料一层层地粘接在打印底板上；最后，完成层间结合与冷冻固化，新挤出的泥料层在一定应力下与上一层泥料层融合在一起，完成层间的融合。当打印5层后，第一层与第二层泥料及其层间实现冷冻固化，后续其它层也自动实现冷冻固化，最终得到生坯，生坯强度不低于300KPa。
将生坯进行冷冻干燥和烧结，得到陶瓷构件。
实施例4
控制打印空间低温氮气吹进量，使得打印空间的气温降低至-40℃。设置浆料挤出速率为0.2cm/s，设置打印层高为0.4mm，设置挤出头移动速率为0.3cm/s。随后，通过电机将配制的氧化硅泥料(将粒径级配为小于200nm的粉体占4％，200nm-1.0μm的粉体占10％，1-10μm的粉体占40％，10-30μm的粉体占30％，大于30μm的粉体占16％的氧化硅陶瓷粉体分散到固含量为25％硅溶胶中，添加0.5％聚乙二醇和1％聚乙烯醇后，球磨8h，获得固含量70％的泥料，泥料的混合溶剂为水)挤出喷嘴，泥料的挤出厚度为0.3mm，泥料一层层地粘接在打印底板上。发现，泥料可以自动地实现层间结合与冷冻固化，但由于打印速度过慢，在打印过程中会出现浆料外溢，最终烧结后得到的产品精度下降。
实施例5
控制打印空间低温氮气吹进量，使得打印空间的气温降低至-40℃。设置浆料挤出速率为3cm/s，设置打印层高为0.4mm，设置挤出头移动速率为0.3cm/s。随后，通过电机将配制的氧化硅泥料(将粒径级配为小于200nm的粉体占4％，200nm-1.0μm的粉体占10％，1-10μm的粉体占40％，10-30μm的粉体占30％，大于30μm的粉体占16％的氧化硅陶瓷粉体分散到固含量为25％硅溶胶中，添加0.5％聚乙二醇和1％聚乙烯醇后，球磨8h，获得固含量70％的泥料，泥料的混合溶剂为水)挤出喷嘴，泥料的挤出厚度为0.3mm。结果发现，由于打印速度过快，生坯会断料或者引入气孔，烧结后的陶瓷构件具有缺陷。
实施例6
控制打印空间低温氮气吹进量，使得打印空间的气温降低至-40℃。设置浆料挤出速率为0.5cm/s，设置打印层高为0.1mm，设置挤出头移动速率为0.3cm/s。随后，通过电机将配制的氧化硅泥料(将粒径级配为小于200nm的粉体占4％，200nm-1.0μm的粉体占10％，1-10μm的粉体占40％，10-30μm的粉体占30％，大于30μm的粉体占16％的氧化硅陶瓷粉体分散到固含量为25％硅溶胶中，添加0.5％聚乙二醇和1％聚乙烯醇后，球磨8h，获得固含量70％的泥料，泥料的混合溶剂为水)挤出喷嘴，泥料的挤出厚度为0.1mm，泥料一层层地粘接在打印底板上。结果发现，泥料可以自动地实现层间结合与冷冻固化，但由于打印高度设置过低，在打印过程中会出现浆料外溢，最终烧结后得到的产品精度下降。
实施例7
控制打印空间低温氮气吹进量，使得打印空间的气温降低至-40℃。设置浆料挤出速率为0.5cm/s，设置打印层高为1.5mm，设置挤出头移动速率为0.3cm/s。随后，通过电机将配制的氧化硅泥料(将粒径级配为小于200nm的粉体占4％，200nm-1.0μm的粉体占10％，1-10μm的粉体占40％，10-30μm的粉体占30％，大于30μm的粉体占16％的氧化硅陶瓷粉体分散到固含量为25％硅溶胶中，添加0.5％聚乙二醇和1％聚乙烯醇后，球磨8h，获得固含量70％的泥料，泥料的混合溶剂为水)挤出喷嘴，泥料的挤出厚度为1mm，泥料一层层地粘接在打印底板上。结果发现，由于打印层高设置过高，浆料挤出量跟不上，导致胚体坍塌。
最后应说明的是：以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。

Claims (10)

1.一种3D冷冻打印方法，其特征在于，所述方法包括：
调控打印空间温度的步骤：将打印空间的温度降低至-40℃至-80℃；
设定打印参数的步骤：设置浆料挤出速率和打印层高；设置挤出头移动速率；
所述浆料挤出速率为0.5cm/s至2cm/s；
所述打印层高为0.4mm至1mm；
所述挤出头移动速率为0.3cm/s至1.5cm/s，确保上下两层完成挤压融合的时间间隙为15-40s；
挤出打印的步骤：将泥料挤出，使泥料一层层地粘接在打印底板上；
层间结合与冷冻固化的步骤：层层泥料自动完成层间结合和冷冻固化。
2.根据权利要求1所述的方法，其特征在于，
通过控制打印空间冷气吹进量对打印空间的温度进行调控。
3.根据权利要求2所述的方法，其特征在于，
所述冷气为液氮汽化后的低温氮气。
4.根据权利要求1所述的方法，其特征在于，
所述泥料包含陶瓷粉体和混合溶剂；
所述陶瓷粉体选自氧化硅、氧化铝、氧化锆、氮化硅、氮化铝中的任一种或多种；
所述混合溶剂为水。
5.根据权利要求1所述的方法，其特征在于，
所述泥料还包含助剂；
所述助剂为硅溶胶、聚乙二醇、聚乙烯醇中的任一种或多种。
6.根据权利要求1所述的方法，其特征在于，
所述泥料的挤出厚度为0.3-1mm。
7.根据权利要求1所述的方法，其特征在于，
泥料通过层间结合和冷冻固化后形成生坯，所述生坯的强度300KPa。
8.根据权利要求1所述的方法，其特征在于，
所述方法还包括：
冷冻干燥的步骤：将生坯冷冻干燥；
烧结的步骤：将冷冻干燥后的生坯烧结。
9.根据权利要求8所述的方法，其特征在于，
在烧结前，对冷冻干燥后的生坯进行表面处理。
10.根据权利要求9所述的方法，其特征在于，
所述表面处理为打磨。
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