CN115368123A - 用于连续3d打印的陶瓷浆料及其制备方法、打印方法 - Google Patents
用于连续3d打印的陶瓷浆料及其制备方法、打印方法 Download PDFInfo
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- CN115368123A CN115368123A CN202211314865.6A CN202211314865A CN115368123A CN 115368123 A CN115368123 A CN 115368123A CN 202211314865 A CN202211314865 A CN 202211314865A CN 115368123 A CN115368123 A CN 115368123A
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- Inorganic Chemistry (AREA)
Abstract
本发明公开了一种用于连续3D打印的陶瓷浆料及其制备方法、打印方法，属于3D打印技术领域，以体积百分比计，该陶瓷浆料包括陶瓷粉末40‑70%和其它组分30‑60%；其中，所述其它组分包括光聚合预聚物、热聚合预聚物、光引发剂、热固化剂和分散剂，所述光聚合预聚物和所述热聚合预聚物的质量含量成预设比例，所述光引发剂含量为所述光聚合预聚物质量的1‑6%，所述热固化剂含量为所述热聚合预聚物质量的5‑80%，所述分散剂含量为所述陶瓷粉末质量的0.5‑3%。本发明通过在光固化过程中调节陶瓷浆料固化程度，减小成形零件与离型膜间的分离力，实现陶瓷浆料连续打印，提高陶瓷零件的打印效率。
Description
技术领域
本发明涉及3D打印技术领域，尤其涉及一种用于连续3D打印的陶瓷浆料及其制备方法、打印方法。
背景技术
数字光处理（DLP，Digital Light Processing）3D打印技术可以可实现复杂结构陶瓷零件的近净成形，且无需模具，可以有效克服陶瓷关键构件设计与制造工艺的巨大局限性，目前被广泛应用于复杂陶瓷零件成形，尤其是在航天航空、生物医学、机械电子等复杂异形陶瓷零件制造领域。
但目前数字光处理3D打印是基于逐层堆积成形，制造的零件存在明显的台阶，表面质量差，限制了数字光处理技术在陶瓷成形领域的进一步应用。且在逐层打印过程中需要成形平台往复运动，成形零件和底面之间的界面分离力较大，限制了DLP的打印速度，存在打印效率低的问题。
发明内容
本发明的主要目的在于提供一种用于连续3D打印的陶瓷浆料及其制备方法、打印方法，旨在解决数字光处理3D打印过程中陶瓷浆料打印效率低和表面质量差的问题。
为实现上述目的，本发明提供一种用于连续3D打印的陶瓷浆料，以体积百分比计，包括陶瓷粉末40-70%和其它组分30-60%；
其中，所述其它组分包括光聚合预聚物、热聚合预聚物、光引发剂、热固化剂和分散剂，所述光聚合预聚物和所述热聚合预聚物的质量含量成预设比例，所述光引发剂含量为所述光聚合预聚物质量的1-6%，所述热固化剂含量为所述热聚合预聚物质量的5-80%，所述分散剂含量为所述陶瓷粉末质量的0.5-3%。
可选地，所述预设比例的调节范围为1:9-9:1。
可选地，所述陶瓷粉末为氧化硅、氧化锆、氧化铝、羟基磷灰石、磷酸三钙、碳化硅、氮化硅和氮化硼中的至少一种。
可选地，所述光聚合预聚物为丙烯酸聚酯树脂、丙烯酸聚氨酯树脂、丙烯酸环氧树脂和丙烯酸聚醚树脂中的至少一种。
可选地，所述热聚合预聚物为不饱和聚酯树脂、环氧树脂、酚醛树脂、三聚氰胺甲醛树脂、呋喃树脂和聚丁二烯树脂中的至少一种。
可选地，所述光引发剂为2,4,6-三甲基苯甲酰基-二苯基氧化膦、2-苯基苄-2-甲基胺-1-（4-吗啉苄苯基）丁酮、2-羟基-2-甲基-1-苯基丙酮、2,4,6-三甲基苯甲酰基苯基膦酸乙酯、1-羟基环己基苯基甲酮、2-甲基-2-（4-吗啉基）-1-[4-（甲硫基）苯基]-1-丙酮、2-二甲氨基-2-苄基-1-[4-（4-吗啉基）苯基]-1-丁酮、2-羟基-2-甲基-1-[4-（2-羟基乙氧基）苯基]-1-丙酮、2-异丙基硫杂蒽酮、2-苯基苄-2-甲基胺-1-（4-吗啉苄苯基）丁酮和苯酰甲酸酯类混合物中至少一种。
可选地，所述热固化剂为脂环族多胺、叔胺、咪唑类、三氟化硼络合物、芳香族多胺、酸酐、甲阶酚醛树脂、氨基树脂、双氰胺和酰肼中的至少一种。
可选地，所述分散剂为硬脂酸、油酸、BYK、KOS110、KOS163、Solsperse 2000、迪高685、聚乙烯基吡啶酮、聚丙烯酸钠、聚丙氧基季三元氯化铵、聚丙烯酸酯铵、γ-氨丙基三乙氧基硅烷、γ-缩水甘油醚氧丙基三甲氧基硅烷和γ-甲基丙烯酰氧基丙基三甲氧基硅烷中的至少一种。
此外，为实现上述目的，本发明还提供一种用于连续3D打印的陶瓷浆料制备方法，用于制备如上文所述的陶瓷浆料，所述制备方法包括以下步骤：
按照所述预设比例配置所述光聚合预聚物和所述热聚合预聚物的预混液；
向所述预混液中依次加入含量为所述光聚合预聚物质量的1-6%的光引发剂、含量为所述热聚合预聚物质量的5-80%的热固化剂和含量为所述陶瓷粉末质量的0.5-3%的分散剂，进行磁力搅拌，直至混合均匀；
向上一步骤所得混合物中加入体积分数为总体积分数40-70%的陶瓷粉末，以及预设数量的球磨球，在球磨机上球磨2-6h，转速为400-800r/min，每球磨30min，暂停15min；
球磨完成后过滤所述球磨球，得到陶瓷浆料。
此外，为实现上述目的，本发明还提供一种用于连续3D打印的陶瓷浆料打印方法，采用如上文所述的陶瓷浆料进行打印，所述打印方法包括以下步骤：
将所述陶瓷浆料置于3D打印设备的料槽中，按照预设的打印参数连续打印得到陶瓷零件素坯，打印过程中成形速率不低于1mm/min；
将所述陶瓷零件素坯置于烘干箱中进行热处理，热处理温度为50-350℃，热处理时间为0.5-4h，得到陶瓷打印件。
本发明提供的用于连续3D打印的陶瓷浆料及其制备方法、打印方法，可以通过调节光聚合预聚物与热聚合预聚物的比例控制光固化程度，来减小成形零件与离型膜间的界面分离力，使得打印过程连续进行，实现陶瓷浆料连续打印，从而提高打印效率，且连续打印过程得到的打印件层间无明显分界，表面质量也得到提升，光热两步固化的方式，可显著减小在DLP光固化成形过程中的热量，实现大尺寸陶瓷零件成形，同时还可减小在DLP光固化成形过程中固化变形，有利于打印高精度陶瓷零件，选择对应不同脱脂峰的光聚合预聚物和热聚合预聚物，还可以在烧结过程中减小单位气体排放，避免零件开裂。
附图说明
图1为本发明实施例用于连续3D打印的陶瓷浆料制备方法的流程示意图；
图2为本发明实施例用于连续3D打印的陶瓷浆料打印方法的流程示意图；
图3为本发明实施例用于连续3D打印的陶瓷浆料打印方法中预设比例为5:5时打印零件与离型膜的结合示意图；
图4为本发明实施例用于连续3D打印的陶瓷浆料打印方法中预设比例为3:7时打印零件与离型膜的结合示意图；
图5为本发明实施例用于连续3D打印的陶瓷浆料打印方法中预设比例为3:7时陶瓷零件素坯的热处理过程示意图。
附图标记说明
本发明目的的实现、功能特点及优点将结合实施例，参照附图做进一步说明。
具体实施方式
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。
目前，实现对陶瓷材料的连续打印，一般是利用氧阻聚原理使得离型膜与成形件之间存在一定厚度未固化的液态树脂，降低了成形零件与离型膜之间的界面分离力，或者在成形零件与离型膜间构建一层流动的氟化油。然而，上述技术仅实现了树脂或陶瓷预聚体的连续成形，陶瓷预聚体实质上仍旧为树脂，能够实现的陶瓷材料也非常有限，且在热处理过程中会产生极大的收缩，最终形成的打印件质量不佳。
本发明实施例提供了一种用于连续3D打印的陶瓷浆料制备方法，如图1所示，该方法包括以下步骤：
步骤S10，按照所述预设比例配置所述光聚合预聚物和所述热聚合预聚物的预混液。
光聚合预聚物可视为在光引发剂和光源的共同作用下可发生光聚合的物质。在光聚合过程中，受光源照射，光引发剂吸收一定波长及强度的光能，发生光物理过程至其激发态，当激发态能量大于断裂键所需能量时，产生自由基，引发光聚合预聚物产生交联固化。
本实施例使用的光聚合预聚物可以为丙烯酸聚酯树脂、丙烯酸聚氨酯树脂、丙烯酸环氧树脂和丙烯酸聚醚树脂中的至少一种。与光聚合预聚物相匹配，使用的光引发剂可以为2,4,6-三甲基苯甲酰基-二苯基氧化膦、2-苯基苄-2-甲基胺-1-（4-吗啉苄苯基）丁酮、2-羟基-2-甲基-1-苯基丙酮、2,4,6-三甲基苯甲酰基苯基膦酸乙酯、1-羟基环己基苯基甲酮、2-甲基-2-（4-吗啉基）-1-[4-（甲硫基）苯基]-1-丙酮、2-二甲氨基-2-苄基-1-[4-（4-吗啉基）苯基]-1-丁酮、2-羟基-2-甲基-1-[4-（2-羟基乙氧基）苯基]-1-丙酮、2-异丙基硫杂蒽酮、2-苯基苄-2-甲基胺-1-（4-吗啉苄苯基）丁酮和苯酰甲酸酯类混合物中至少一种。上述光引发剂可在波长200-800nm的光照射下引发光聚合预聚物产生聚合交联反应。
热聚合预聚物可视为在加热作用下可进行单体聚合的物质。在热聚合过程中，加热作用促使单体激发变为单体自由基，进而产生交联聚合。热聚合过程中还可以加入热固化剂进一步促进热聚合预聚体的交联聚合。
本实施例使用的热聚合预聚物可以为不饱和聚酯树脂、环氧树脂、酚醛树脂、三聚氰胺甲醛树脂、呋喃树脂和聚丁二烯树脂中的至少一种。与热聚合预聚物向匹配，使用的热固化剂可以为脂环族多胺、叔胺、咪唑类、三氟化硼络合物、芳香族多胺、酸酐、甲阶酚醛树脂、氨基树脂、双氰胺和酰肼中的至少一种。上述热固化剂可以在50-350℃的温度范围内促进热聚合预聚物的交联聚合。
光聚合预聚物和热聚合预聚物的加入比例可在1:9-9:1的范围内进行调节。
步骤S20，向所述预混液中依次加入含量为所述光聚合预聚物质量的1-6%的光引发剂、含量为所述热聚合预聚物质量的5-80%的热固化剂和含量为所述陶瓷粉末质量的0.5-3%的分散剂，进行磁力搅拌，直至混合均匀。
分散剂可以使陶瓷粉末在浆料中分散均匀，同时防止陶瓷颗粒的沉降。本实施例使用的分散剂可以为硬脂酸、油酸、BYK、KOS110、KOS163、Solsperse 2000、迪高685、聚乙烯基吡啶酮、聚丙烯酸钠、聚丙氧基季三元氯化铵、聚丙烯酸酯铵、γ-氨丙基三乙氧基硅烷、γ-缩水甘油醚氧丙基三甲氧基硅烷和γ-甲基丙烯酰氧基丙基三甲氧基硅烷中的至少一种。磁力搅拌的时间可以为10-30min。
步骤S30，向上一步骤所得混合物中加入体积分数为总体积分数40-70%的陶瓷粉末，以及预设数量的球磨球，在球磨机上球磨2-6h，转速为400-800r/min，每球磨30min，暂停15min。
本实施例使用的陶瓷粉末可以为氧化硅、氧化锆、氧化铝、羟基磷灰石、磷酸三钙、碳化硅、氮化硅和氮化硼中的至少一种，粉末粒径为100nm-20μm。不同种类的陶瓷粉末之间密度差异较大，当浆料中陶瓷粉末的体积分数低于40%时，成形的零件烧结收缩率大，力学性能差。球磨过程中的暂停可以防止长时间球磨温度过高使得热聚合预聚物固化交联。
步骤S40，球磨完成后过滤所述球磨球，得到陶瓷浆料。
制备得到的陶瓷浆料粘度在10Pa·s以下。
本发明实施例还提供一种用于连续3D打印的陶瓷浆料打印方法，如图2所示，该打印方法包括以下步骤：
步骤S50，将所述陶瓷浆料置于3D打印设备的料槽中，按照预设的打印参数打印得到陶瓷零件素坯，打印过程中成形速率不低于1mm/min。
使用光固化3D打印方法打印陶瓷浆料，打印设备可以包含设置于料槽底部的光源，以及可在垂直方向上往返运动的成形平台，料槽底部可以设置离型膜，离型膜将陶瓷浆料与料槽底部隔离开来。
图3为预设比例为5:5时打印零件与离型膜的结合示意图，如图3所示，在打印过程中，光源6从料槽底部透过离型膜5照射陶瓷浆料，浆料中的光聚合预聚物1之间发生交联固化，形成光聚合预聚物的交联结合4，光聚合预聚物1和离型膜5之间也形成物理粘结点位，使陶瓷浆料与离型膜5粘结。图4为预设比例为3:7时打印零件与离型膜的结合示意图，如图4所示，当热聚合预聚物2含量高于光聚合预聚物1时，光聚合预聚物1的排列更为稀疏，与离型膜5之间的结合点位减少，界面分离力降低，可实现连续打印，成形速率提升。
步骤S60，将所述陶瓷零件素坯置于烘干箱中进行热处理，热处理温度为50-350℃，热处理时间为0.5-4h，得到陶瓷打印件。
打印完成得到陶瓷零件素坯后，可以进行热处理以提高其强度。图5为预设比例为3:7时陶瓷零件素坯热处理示意图，如图5所示，打印完成后陶瓷零件素坯与离型膜分离，在热处理过程中，热聚合预聚物2在50-350℃的温度下交联固化，形成热聚合预聚物的交联结合7，陶瓷零件素坯的固化程度得到进一步的提高，其强度也随之提高。
陶瓷浆料中包含的光聚合预聚物和热聚合预聚物，在后续的烧结过程中可对应不同的脱脂峰，从而减小单位气体的排放，避免零件开裂。比如，光聚合预聚物和热聚合预聚物比例为6:4时，其中光聚合预聚物选择1,6-己二醇二丙烯酸酯和三羟甲基丙烷三丙烯酸酯两种丙烯酸聚酯树脂，比例为1:1，热聚合预聚物为环氧树脂E51，热固化剂为甲基六氢邻苯二甲酸酐（酸酐类），热聚合预聚物和热固化剂比例为100:80，陶瓷粉末为二氧化硅，粒径D50=1um，陶瓷粉末所占体积分数为40%，光引发剂为2,4,6-三甲基苯甲酰基-二苯基氧化膦，含量光聚合物预聚物质量的3 %，分散剂为迪高685，含量为陶瓷粉末质量的2.5%，球磨后，粘度为500 mPa·s。在烧结过程中光聚合预聚物环氧树脂E51的分解温度180-250℃，而光聚合预聚物1,6-己二醇二丙烯酸酯和三羟甲基丙烷三丙烯酸酯混合树脂分解温度主要在475-515℃，因此在烧结过程中光聚合预聚物环氧树脂E51可在较低温度下分解，产生一定量气体排出，同时被优先分解的光聚合预聚物环氧树脂E51还可形成气体通道，在较高温度为光聚合预聚物1,6-己二醇二丙烯酸酯和三羟甲基丙烷三丙烯酸酯混合树脂分解提供气体通道，有利于气体排出，通时由于分解温度区间错开，减小了单位体积内气体排放，减小了烧结过程中产生气体对零件的冲击，可避免零件开裂。
本发明提供的用于连续3D打印的陶瓷浆料及其制备方法、打印方法，可以通过调节光聚合预聚物与热聚合预聚物的比例控制光固化程度，来减小成形零件与离型膜间的界面分离力，使得打印过程连续进行，实现陶瓷浆料连续打印，从而提高打印效率，且连续打印过程得到的打印件层间无明显分界，表面质量也得到提升，光热两步固化的方式，可显著减小在DLP光固化成形过程中的热量，实现大尺寸陶瓷零件成形，以及减小在DLP光固化成形过程中固化变形，有利于打印高精度陶瓷零件，选择对应不同脱脂峰的光聚合预聚物和热聚合预聚物，还可以在烧结过程中减小单位气体排放，避免零件开裂。
需要说明的是，在本文中，术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程、方法、物品或者系统不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者系统所固有的要素。在没有更多限制的情况下，由语句“包括一个……”限定的要素，并不排除在包括该要素的过程、方法、物品或者系统中还存在另外的相同要素。
上述本发明实施例序号仅仅为了描述，不代表实施例的优劣。
以上仅为本发明的优选实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书及附图内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。
Claims (10)
1.一种用于连续3D打印的陶瓷浆料，其特征在于，以体积百分比计，包括陶瓷粉末40-70%和其它组分30-60%；
其中，所述其它组分包括光聚合预聚物、热聚合预聚物、光引发剂、热固化剂和分散剂，所述光聚合预聚物和所述热聚合预聚物的质量含量成预设比例，所述光引发剂含量为所述光聚合预聚物质量的1-6%，所述热固化剂含量为所述热聚合预聚物质量的5-80%，所述分散剂含量为所述陶瓷粉末质量的0.5-3%。
2.如权利要求1所述的用于连续3D打印的陶瓷浆料，其特征在于，所述预设比例的调节范围为1:9-9:1。
3.如权利要求1所述的用于连续3D打印的陶瓷浆料，其特征在于，所述陶瓷粉末为氧化硅、氧化锆、氧化铝、羟基磷灰石、磷酸三钙、碳化硅、氮化硅和氮化硼中的至少一种。
4.如权利要求1所述的用于连续3D打印的陶瓷浆料，其特征在于，所述光聚合预聚物为丙烯酸聚酯树脂、丙烯酸聚氨酯树脂、丙烯酸环氧树脂和丙烯酸聚醚树脂中的至少一种。
5.如权利要求1所述的用于连续3D打印的陶瓷浆料，其特征在于，所述热聚合预聚物为不饱和聚酯树脂、环氧树脂、酚醛树脂、三聚氰胺甲醛树脂、呋喃树脂和聚丁二烯树脂中的至少一种。
6.如权利要求1所述的用于连续3D打印的陶瓷浆料，其特征在于，所述光引发剂为2,4,6-三甲基苯甲酰基-二苯基氧化膦、2-苯基苄-2-甲基胺-1-（4-吗啉苄苯基）丁酮、2-羟基-2-甲基-1-苯基丙酮、2,4,6-三甲基苯甲酰基苯基膦酸乙酯、1-羟基环己基苯基甲酮、2-甲基-2-（4-吗啉基）-1-[4-（甲硫基）苯基]-1-丙酮、2-二甲氨基-2-苄基-1-[4-（4-吗啉基）苯基]-1-丁酮、2-羟基-2-甲基-1-[4-（2-羟基乙氧基）苯基]-1-丙酮、2-异丙基硫杂蒽酮、2-苯基苄-2-甲基胺-1-（4-吗啉苄苯基）丁酮和苯酰甲酸酯类混合物中至少一种。
7.如权利要求1所述的用于连续3D打印的陶瓷浆料，其特征在于，所述热固化剂为脂环族多胺、叔胺、咪唑类、三氟化硼络合物、芳香族多胺、酸酐、甲阶酚醛树脂、氨基树脂、双氰胺和酰肼中的至少一种。
8.如权利要求1所述的用于连续3D打印的陶瓷浆料，其特征在于，所述分散剂为硬脂酸、油酸、BYK、KOS110、KOS163、Solsperse 2000、迪高685、聚乙烯基吡啶酮、聚丙烯酸钠、聚丙氧基季三元氯化铵、聚丙烯酸酯铵、γ-氨丙基三乙氧基硅烷、γ-缩水甘油醚氧丙基三甲氧基硅烷和γ-甲基丙烯酰氧基丙基三甲氧基硅烷中的至少一种。
9.一种用于连续3D打印的陶瓷浆料制备方法，其特征在于，用于制备如权利要求1-8任一项所述的陶瓷浆料，所述制备方法包括以下步骤：
按照所述预设比例配置所述光聚合预聚物和所述热聚合预聚物的预混液；
向所述预混液中依次加入含量为所述光聚合预聚物质量的1-6%的光引发剂、含量为所述热聚合预聚物质量的5-80%的热固化剂和含量为所述陶瓷粉末质量的0.5-3%的分散剂，进行磁力搅拌，直至混合均匀；
向上一步骤所得混合物中加入体积分数为总体积分数40-70%的陶瓷粉末，以及预设数量的球磨球，在球磨机上球磨2-6h，转速为400-800r/min，每球磨30min，暂停15min；
球磨完成后过滤所述球磨球，得到陶瓷浆料。
10.一种用于连续3D打印的陶瓷浆料打印方法，其特征在于，采用如权利要求1-8任一项所述的陶瓷浆料进行打印，所述打印方法包括以下步骤：
将所述陶瓷浆料置于3D打印设备的料槽中，按照预设的打印参数连续打印得到陶瓷零件素坯，打印过程中成形速率不低于1mm/min；
将所述陶瓷零件素坯置于烘干箱中进行热处理，热处理温度为50-350℃，热处理时间为0.5-4h，得到陶瓷打印件。
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