CN108409311B - 一种多组分3d打印挤出成型材料 - Google Patents

一种多组分3d打印挤出成型材料 Download PDF

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CN108409311B
CN108409311B CN201810199204.0A CN201810199204A CN108409311B CN 108409311 B CN108409311 B CN 108409311B CN 201810199204 A CN201810199204 A CN 201810199204A CN 108409311 B CN108409311 B CN 108409311B
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杨道媛
滕仪宾
刘莹
梁威威
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Zhengzhou University
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Abstract

本发明提供一种多组分3D打印挤出成型材料，所述成型材料由N种组分混配而成且N≥2，所述N种组分均包括耐火材料粉、分散剂和水，且N种组分中的至少一种还包括调凝剂，N种组分中的任m种组分还包括粘结剂，其余N‑m种组分中的至少一种组分还包括固化剂。本发明不仅能够延长成型材料的保质期，而且能够提供不同固化时间或不同温度条件应用的系列产品。

Description

一种多组分3D打印挤出成型材料
技术领域
本发明属于3D打印材料技术领域，具体涉及一种多组分3D打印挤出成型材料。
背景技术
快速成型，也被称为增材制造，基本原理是基于电脑和互联网的数字化立体技术，将一项设计物品转化为3D数字模型，然后采用分层加工、叠加成形，即通过逐层增加材料来打印成3D实体，由此把计算机上的蓝图变成实物，在成本、速度和精确度上都远胜于传统制造技术，尤其适合于个性化定制。
耐火材料的3D打印成型技术包括激光选区烧结成型技术、光固化快速成型技术、融化沉积成型技术、自由挤出成型技术等。自由挤出成型技术指通过机械压力或气压将物料挤出，并随着三维运动沉积到指定位置，这项技术要求物料能够连续挤出，并在适当的时间内固化，使得挤出后的材料能在一定的跨度上维持形状，满足耐火材料制备过程中形状设计个性化的需求。
但是，由于耐火材料的结构和其键性的原因，致使耐火材料本身的塑性较差，通常无法直接用于3D打印挤出成型，且沉积后难以维持形状，因此耐火材料在用于3D打印时，通常需要加入助剂配成3D打印成型材料，但是助剂的加入却不利于成型材料的长期储存。
专利CN106810200A公开了一种双组分陶瓷3D打印挤出成型材料，材料组分包括A组分和B组分，其中A组分为陶泥与粘接剂的混合物，B组分为陶泥与固化剂的混合物；材料形状为浆料；打印时，将陶瓷浆料A组分和B组分混料打印陶瓷坯体即可，该专利将成型材料分成两个组分分别制作保存，延长了材料的保存时间，而打印时则加速了产品的固化，提高了打印的速度。但是产品形式单一，不能满足3D打印中的多种工艺要求。
发明内容
本发明针对现有技术中存在的问题，提供一种多组分3D打印挤出成型材料，不仅能够延长成型材料的保质期，而且能够提供不同固化时间或不同温度条件应用的系列产品。
本发明采用如下技术方案：
一种多组分3D打印挤出成型材料，所述成型材料由N种组分混配而成且N≥2，所述N种组分均包括耐火材料粉、分散剂和水，且N种组分中的至少一种还包括调凝剂，N种组分中的任m种组分还包括粘结剂，其余N-m种组分中的至少一种组分还包括固化剂，即粘结剂和固化剂不能同时用于同一组分中。具体到各组分中，为保证各组分良好的分散和成型效果，当含有某种成分时，该成分优选以下用量，在任一组分中，以该组分的总重计，粘结剂4％-6％，分散剂0.16％-1％，调凝剂0.01％-0.08％，固化剂0.01％-0.08％，水7％～20％，余量均为耐火材料粉；且当粘结剂和分散剂同时用在同一组分中时，当粘结剂用量较多时，分散剂用量可有所减少；如无特别说明，本发明所涉及百分比均为重量百分比。
优选地，所述耐火材料粉包括氧化铝、氧化锆、氧化镁、氧化硅、氮化硅、碳化硅、莫来石、镁铝尖晶石，锆刚玉、矾土或镁砂中的一种或多种，具体到耐火材料粉的配合比例，本领域技术人员可以根据耐火材料的性能要求进行灵活调整。
优选地，所述耐火材料粉采用级配构成。
优选地，所述级配的具体方法为：在1000重量份的耐火材料粉中，
粒度0.5-1mm 200-300份；
粒度30-200μm 250-350份；
粒度5-10μm 100-200份；
粒度1.2-3μm 200-350份。
优选地，N种组分混配时，任两组分之间的重量比为1∶1～1.5。
优选地，所述调凝剂选用氢氧化钠、氢氧化钾或质量分数为20～30％的氨水。
优选地，所述粘结剂选用聚丙烯酰胺、羧甲基纤维素、聚乙烯醇或纤维素钠。
优选地，所述分散剂选用三聚磷酸钠、六偏磷酸钠、柠檬酸、油酸和聚乙二醇的一种或两种。
优选地，所述固化剂选用乙二醛。
本发明的有益效果如下：
(1)本发明耐火材料粉需要采用颗粒级配，这样可以使小颗粒粉末填充大颗粒的空隙，以便于获得更大的密度，合理的级配既有利于获得高流动性从而易于挤出成型，也有利于坯体烧结后获得高密度、高强度的制品，提高材料的抗渣性能，更为重要的是，这种级配构成保证了坯体烧结过程中的体积变化小，形状保持性好避免裂纹的产生，同时有利于提高材料的热震稳定性；据测试，本发明所述得到的3D打印产品的收缩率明显降低，同时强度得到显著提高，这使得3D打印耐火陶瓷的实际应用迈进一大步。
(2)本发明采用的分散剂主要是避免耐火材料粉之间的凝聚，提高分散性，以便更好地发挥耐火材料粉的作用；采用的粘结剂主要是提供成型材料的粘结作用，以便能够打印出预设形状并能够在打印过程中保持形状；固化剂主要是提供成型材料的固化作用，以便打印出坯体后快速固化保持形状；采用的调凝剂主要是配合固化剂调整成型材料的固化时间，以适应不同的打印温度等工艺要求；
(3)本发明在延长成型材料的保质期的基础之上，提供了多种形式的成型材料品种组合，例如将耐火材料粉与分散剂的混合组分，特点是耐火材料粉的分散性佳，调凝剂和耐火材料粉的混合组分，与含固化剂的混合组分分开进料，可以实现不同的固化时间，以满足不同温度条件的应用，此外还可以根据耐火产品的性能要求进行不同种类耐火材料粉的混配或者按照耐火材料的要求设计不同组分的加料顺序；
(4)本发明采用多组分分开进料的方式，一方面有利于成型材料的原料存储，保质期长，更为重要的是，多组分混合后的固化时间可以根据具体的工艺需求进行调整，理论上来说，调凝剂的用量增多会缩短固化时间，固化剂的用量增多也会缩短固化时间，由此能够有效地扩展挤出打印机的应用范围；
(5)本发明提供的成型材料制备方法简单，且耐火材料来源广泛，成本低，有利于3D打印混合料的推广，对耐火材料3D打印技术的发展有着明显的促进作用，也有利于高温窑炉技术的智能化发展。
附图说明
图1为应用例得到的立方坯体。
具体实施方式
为了使本发明的技术目的、技术方案和有益效果更加清楚，下面结合附图和具体实施例对本发明的技术方案作出进一步的说明。
实施例1
一种3D打印用挤出成型材料，该成型材料设计为双组分料，所述双组分料由A组分和B组分构成，A组分和B组分分别通过气泵压力作用输入打印机的混料仓，混合均匀后制备出3D打印用双组分混合料；
其中，所述A组分和B组分通过如下方法制备，以重量份数计：
第一步，取200份粒度0.5-1mm的氧化铝粉、350份粒度30-200μm氧化铝粉、100份粒度5-10μm氧化铝粉、350份粒度1.2-3μm氧化铝粉；
第二步，将称取好的以上四种粉加入到转速为200转/分种的球磨罐中球磨1h，得到混合粉末材料；
第三步，以重量份数计，A组分由80份的混合粉末材料、6份的聚丙烯酰胺、0.2份的六偏磷酸钠、0.08份的氢氧化钠以及13.72份蒸馏水混合配制而成，其中聚丙烯酰胺、六偏磷酸钠和氢氧化钠优选先均匀分散于上述蒸馏水中，再与混合粉末材料进行混合，由此使得A组分中的各成分混合更为均匀充分；
第四步，以重量份数计，B组分由120份的混合粉末材料、1.5份的三聚磷酸钠、0.07份的乙二醛以及28.43份蒸馏水混合配制而成，其中三聚磷酸钠和乙二醛优选先均匀分散于上述蒸馏水中，再与混合粉末材料进行混合，由此使得B组分中的各成分混合更为均匀充分；
挤出打印时，取100份A组分和150份B组分混合构成双组分料，A组分和B组分的质量比为1:1.5，在15℃左右，自混合开始30min后开始凝固，应在30min内进行打印成型。
实施例2
一种3D打印用挤出成型材料，该成型材料设计为三组分料，所述三组分料由A组分、B组分和C组分构成，A组分、B组分和C组分分别通过气泵压力作用输入打印机的混料仓，混合均匀后制备出3D打印用三组分混合料；
其中，所述A、B、C组分通过如下方法制备，以重量份数计：
第一步，取200份粒度0.5-1mm的氧化铝粉、300份粒度30-200μm氧化铝粉、200份粒度5-10μm氧化铝粉、300份粒度1.2-3μm氧化铝粉；
第二步，将称取好的以上四种粉加入到转速为300转/分种的球磨罐中球磨1h，得到混合粉末材料；
第三步，以重量份数计，A组分由86份的混合粉末材料、6份的羧甲基纤维素、0.16份的三聚磷酸钠以及7.84份蒸馏水混合配制而成，其中羧甲基纤维素和三聚磷酸钠优选先均匀分散于上述蒸馏水中，再与混合粉末材料进行混合，由此使得A组分中的各成分混合更为均匀充分；
第四步，以重量份数计，B组分由82份的混合粉末材料、0.5份的六偏磷酸钠、0.5份的聚乙二醇、0.04份的氢氧化钾以及16.96份蒸馏水混合配制而成，其中六偏磷酸钠、聚乙二醇和氢氧化钾优选先均匀分散于上述蒸馏水中，再与混合粉末材料进行混合，由此使得B组分中的各成分混合更为均匀充分；
第五步，以重量份数计，C组分由86份的混合粉末材料、0.5份的油酸、0.06份的乙二醛以及13.44份蒸馏水混合配制而成，其中油酸和乙二醛优选先均匀分散于上述蒸馏水中，再与混合粉末材料进行混合，由此使得C组分中的各成分混合更为均匀充分；
挤出打印时，取70份A组分、60份B组分及70份C组分混合构成三组分料，A组分、B组分和C组分的质量比为7:6:7，在30℃左右，自混合开始15min后开始凝固，应在15min内进行打印成型。
实施例3
一种3D打印用挤出成型材料，该成型材料设计为四组分料，所述四组分料由A组分、B组分、C组分和D组分构成，A组分、B组分、C组分和D组分分别通过气泵压力作用输入打印机的混料仓，混合均匀后制备出3D打印用多组分混合料；
其中，所述A、B、C、D组分通过如下方法制备，以重量份数计：
第一步，取200份粒度0.5-1mm的氧化铝粉、350份粒度30-200μm氧化铝粉、100份粒度5-10μm氧化铝粉、350份粒度1.2-3μm氧化铝粉；
第二步，将称取好的以上四种粉加入到转速为300转/分种的球磨罐中球磨1h，得到混合粉末材料；
第三步，以重量份数计，A组分由85份的混合粉末材料、4份的纤维素钠、0.3份的柠檬酸、0.5份的油酸、0.01份的质量分数为20～30％的氨水以及10.19份蒸馏水混合配制而成，其中纤维素钠和柠檬酸优选先均匀分散于上述蒸馏水中，再与混合粉末材料进行混合，由此使得A组分中的各成分混合更为均匀充分；
第四步，以重量份数计，B组分由85份的混合粉末材料、5份的纤维素钠、0.4份的三聚磷酸钠以及9.6份蒸馏水混合配制而成，其中纤维素钠和三聚磷酸钠优选先均匀分散于上述蒸馏水中，再与混合粉末材料进行混合，由此使得B组分中的各成分混合更为均匀充分；
第五步，以重量份数计，C组分由85份的混合粉末材料、0.6份的三聚磷酸钠、0.05份的氢氧化钠、0.06份的乙二醛以及14.29份蒸馏水混合配制而成，其中三聚磷酸钠、氢氧化钠和乙二醛优选先均匀分散于上述蒸馏水中，再与混合粉末材料进行混合，由此使得C组分中的各成分混合更为均匀充分；
第六步，以重量份数计，D组分由85份的混合粉末材料、1份的三聚磷酸钠、0.08份的乙二醛以及13.92份蒸馏水混合配制而成，其中三聚磷酸钠和乙二醛优选先均匀分散于上述蒸馏水中，再与混合粉末材料进行混合，由此使得D组分中的各成分混合更为均匀充分；
挤出打印时，由100份A组分、100份B组分、100份C组分及100份D组分混合构成四组分料，A组分、B组分、C组分和D组分的质量比为1:1:1:1，在20℃左右，自混合开始22min后开始凝固，应在22min内进行打印成型。
应用例
取实施例1制备的3D打印用双组分料，将A组分和B组分分别装入两个料筒中，分别通过气泵压力作用输入打印机的混料仓，混合均匀后制备出3D打印用双组分混合料，然后进行打印成型，获得40×40×40(mm)的立方坯体，如图1所示，将该坯体分别在1250℃、1350℃、1450℃和1550℃下烧结，烧结后测量各个样品性能，统计结果如表1。
表1不同温度下烧结的3D打印坯体性能
Figure BDA0001593974030000071
对比周攀等人在《粘结剂含量含对三维打印Al2O3基陶瓷材料性能的影响》一文所述打印的3D产品线随粘结剂含量在15％-50％之间变化，收缩率处于在19％-30％、强度处于30MPa-50MPa，显然，本发明所述得到的3D打印产品的收缩率明显降低，同时强度得到显著提高，离3D打印耐火陶瓷的实际应用迈进一大步。
以上所述，仅是本发明的较佳实施例而已，并非对本发明作任何形式上的限制，虽然本发明已以较佳实施例举例如上，然而并非用以限定本发明，任何熟悉本专业的技术人员，在不脱离本发明技术方案范围内，当可利用上述揭示的技术内容作出些许更动或修饰为等同变化的等效实施例，但凡是未脱离本发明技术方案内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均仍属于本发明技术方案的范围内。

Claims (4)

1.一种多组分3D打印挤出成型材料，其特征在于：所述成型材料由N种组分混配而成且N≥2，所述N种组分均包括耐火材料粉、分散剂和水，且N种组分中的至少一种还包括调凝剂，N种组分中的任m种组分还包括粘结剂，其余N-m种组分中的至少一种组分还包括固化剂；粘结剂和固化剂不同时用于同一组分中；
所述耐火材料粉采用级配构成；
所述级配的具体方法为：在1000重量份的耐火材料粉中，
粒度0.5-1mm 200-300份；
粒度30-200μm 250-350份；
粒度5-10μm 100-200份；
粒度1.2-3μm 200-350份；
任一组分中，当含有某成分时，该成分的含量为：以该组分的总重计，粘结剂4%-6%，分散剂0.16%-1%，调凝剂 0.01%-0.08%，固化剂 0.01%-0.08%；
所述调凝剂选用氢氧化钠、氢氧化钾或氨水；
所述粘结剂选用聚丙烯酰胺、羧甲基纤维素、聚乙烯醇或纤维素钠；
所述分散剂选用三聚磷酸钠、六偏磷酸钠、柠檬酸、油酸和聚乙二醇中的一种或两种；
所述固化剂选用乙二醛。
2.根据权利要求1所述的多组分3D打印挤出成型材料，其特征在于：所述耐火材料粉包括氧化铝、氧化锆、氧化镁、氧化硅、氮化硅、碳化硅、莫来石、镁铝尖晶石、锆刚玉、矾土和镁砂中的一种或多种。
3.根据权利要求1所述的多组分3D打印挤出成型材料，其特征在于，N种组分混配时，任两组分之间的重量比为1∶1~1.5。
4.根据权利要求1所述的多组分3D打印挤出成型材料，其特征在于，该成型材料设计为双组分料，所述双组分料由A组分和B组分构成，其中，所述A组分和B组分通过如下方法制备，以重量份数计：
第一步，取200份粒度0.5-1mm的氧化铝粉、350份粒度30-200μm氧化铝粉、100份粒度5-10μm氧化铝粉、350份粒度1.2-3μm氧化铝粉；
第二步，将称取好的以上四种粉加入到转速为200转/分种的球磨罐中球磨1h，得到混合粉末材料；
第三步，以重量份数计，A组分由80份的混合粉末材料、6份的聚丙烯酰胺、0.2份的六偏磷酸钠、0.08份的氢氧化钠以及13.72份蒸馏水混合配制而成，其中聚丙烯酰胺、六偏磷酸钠和氢氧化钠先均匀分散于上述蒸馏水中，再与混合粉末材料进行混合，由此使得A组分中的各成分混合更为均匀充分；
第四步，以重量份数计，B组分由120份的混合粉末材料、1.5份的三聚磷酸钠、0.07份的乙二醛以及28.43份蒸馏水混合配制而成，其中三聚磷酸钠和乙二醛先均匀分散于上述蒸馏水中，再与混合粉末材料进行混合，由此使得B组分中的各成分混合更为均匀充分；
挤出打印时，取100份A组分和150份B组分混合构成双组分料，A组分和B组分的质量比为1:1.5，在15℃，自混合开始30min后开始凝固，应在30min内进行打印成型。
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