CN111590877A - 一种基于近红外光聚合的墨水直写三维打印的方法 - Google Patents
一种基于近红外光聚合的墨水直写三维打印的方法 Download PDFInfo
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Abstract
本发明涉及一种基于近红外光聚合的墨水直写三维打印的方法技术,属于材料加工技术领域。所述方法为:直写喷头在三维空间中运动或静止,墨水从直写喷头中被挤出,在接受近红外光的照射,固化后完成三维物体成型,并且固化时间t不超过近红外光直径dl与墨水挤出速度vi比值,即t≤dl/vi。由于近红外光具有较好的介质穿透性,在成型中能穿透结构促进内外部均达到较高的固化程度,从而能够实现跨尺度结构的3D打印,并且本发明所提供的方法精准的控制了墨水被固化过程,从而实现DIW阵列式3D结构的实时固化。
Description
技术领域
本发明涉及一种基于近红外光聚合的墨水直写三维打印的方法技术,属于材料加工技术领域。
背景技术
当前3D打印技术主要面向于金属材料、陶瓷材料以及聚合物材料;其中聚合物材料的3D打印成型方式通常通过热辅助或光辅助进行。直写技术(DIW,Direct Ink Writing)常用作3D打印的实施方法,可利用热固性或光固性3D打印油墨实现增材制造,在微结构成型、智能器件制备等领域已有大量应用。
当前基于DIW的3D打印使用的油墨通常为热固化型或紫外光(UV)固化型。其中对于热固化型油墨,当成型大直径特征尺寸的线条或大体积形体中,由于油墨自身重力影响,结构容易出现缺陷或塌陷,因而热固化型油墨受限于小尺寸3D打印中应用。
而另一方面,对于光固化型油墨,当前通常使用紫外光(UV)或蓝光作为光源配合DIW进行实时固化,然而由于这些光波长较短,穿透力较弱,辐照大直径特征尺寸线条中易造成线芯部分固化程度较低而不利于机械性能;此外由于光源难以同时覆盖多个结构并快速固化,因而紫外光固化型难以实现DIW阵列式打印以提高打印效率。
发明内容
基于上述问题,本发明提供了一种基于近红外光聚合的墨水直写三维打印的方法,所述方法为:直写喷头在三维空间中运动或静止,墨水从直写喷头中被挤出,在接受近红外光的照射,固化后完成三维物体成型,并且固化时间t不超过近红外光直径dl与浆料挤出速度vi比值,即t≤dl/vi。
在一种实施方式中,所述直写喷头的运动速度为0~5.0mm/s,所述直写喷头的直径范围为0.1μm~10㎝。
在一种实施方式中,所述墨水的组成包括可光聚合树脂、可光聚合单体、光引发剂、上转换材料、触变剂、填料。
在一种实施方式中,所述墨水的组成如下:
可光聚合树脂0-80wt%、可光聚合单体0-80wt.%、光引发剂0.5-6wt%、上转换材料0.5-5wt%、触变剂0-30wt.%、填料2-30wt%。
在一种实施方式中,所述墨水的流变性能要满足:弹性模量G’为损耗模量G”的0.5~5
倍,即0.5G”≤G’≤5G”。
在一种实施方式中,所述挤出墨水的作用力为压力,所述压力不超过800kPa。
在一种实施方式中,所述近红外激光为光束或光斑,并且光斑或光束位于直写喷头1厘米空间内。
在一种实施方式中,所述近红外激光的功率为0-50W,波段范围为700-2000nm。
在一种实施方式中,所述可光聚合树脂包括含丙烯酸酯双键的树脂、含乙烯基醚双键的树脂、含环氧基团的树脂,优选为含丙烯酸酯双键的树脂;
可光聚合单体包括单官能丙烯酸酯类单体、双官丙烯酸酯类单体、多官能丙烯酸酯类单体、乙烯基醚类单体、酯环族环氧类单体、氧杂环丁烷类单体中的一种或多种;
光引发剂包括2,4,6-三甲基苯甲酰二苯基氧化膦、1-羟基环己基苯基甲酮、2,4,6-三甲基苯甲酰基苯基膦酸乙酯、双2,6-二氟-3-吡咯苯基二茂钛、苯基双(2,4,6-三甲基苯甲酰基)氧化膦、2-异丙基硫杂蒽酮、2-羟基-2-甲基-1-苯基丙酮、2-甲基-2-(4-吗啉基苯基)-1-[4-(甲硫基)苯基]-1-丙酮、1,7,7'-三甲基-双环(2,2,1)庚烷-1,3-二酮、四氟硼酸甲基二苯基硫鎓盐、4,4'-二甲基二苯基碘鎓盐六氟磷酸盐、二茂铁类六氟磷酸盐中的一种或多种;
上转换材料包括NaYF4、BaYF5、NaGdF4、LiYF4、NaYbF4、Na3ScF6、YF3、GdOF中的一种或多种;
触变剂包括气硅;
填料包括硫酸钡、钛白粉、二氧化硅、滑石粉中的一种或多种。
在一种实施方式中,所述可光聚合树脂包括环氧丙烯酸酯、聚氨酯丙烯酸酯、氨基丙烯酸酯、聚酯丙烯酸酯。
在一种实施方式中,所述墨水中含有颜料。
本发明的第二个目的在于,提供一种基于近红外光聚合的墨水直写三维打印的设备,所述设备包括:
支撑台,用于支撑成型的三维物体;
近红外光发射结构位于支撑台上方,与控制器固定连接,控制器驱动近红外光发射结构运动或静止;
直写喷头位于支撑台上方,直写喷头与墨水储备罐密封连接,直写喷头和/或墨水储备罐与控制器固定连接,控制器驱动直写喷头和墨水储备罐运动或静止。
有益效果
由于近红外光具有较好的介质穿透性,在成型中能穿透结构促进内外部均达到较高的固化程度,从而能够实现从小尺寸到大尺寸结构的3D打印,并且本发明所提供的方法精准的控制了墨水被固化过程,从而实现DIW阵列式3D结构的实时固化。此外由于采用实时固化,在墨水出料过程中便实现固化交联,机械性能提升,避免了储能模量不足造成大尺寸的结构塌陷。此外,相对于传统UV光源,NIR光源具有更好的穿透性,能够充分固化墨水而得到机械性能更可预测且相对较佳的3D打印物件。
附图说明
图1为基于近红外光聚合的墨水直写三维打印的设备,其中1为支撑台;2为近红外光发射结构;3为控制器;4为直写喷头;5为墨水储备罐;6为打印出的三维物体。
图2为使用不同直径测定所得样品的转化率及其形貌的超景深显微镜图像。
图3为未采用近红外实时固化所得样品和采用近红外实时固化所得样品显微镜对比图像。
图4为混有不同颜料的墨水打印所得样品的转化率及其形貌的超景深显微镜图像。
图5为实施例所用的引发剂Iragacure 784及四种颜料的紫外-可见光吸收光谱图。
图6的a、b分别为实施例4中采用两种颜色墨水进行同轴打印所得内外具有不同颜色的样品图和截面图。
图7的a、b分别为实施例5中得到的具有悬空结构的两个不同3D打印形体。
具体实施方式
实施例1:
图1为近红外光聚合的墨水直写三维打印的设备,该设备由支撑台1、近红外光发射结构2、控制器3、直写喷头4、墨水储备罐5组成。
其中支撑台1,用于支撑三维物体6;近红外光发射结构2位于支撑台1上方,与控制器3固定连接,控制器3驱动近红外光发射结构2运动或静止;直写喷头4位于支撑台1上方,直写喷头4与墨水储备罐5密封连接,直写喷头4和墨水储备罐5与控制器3固定连接,控制器3驱动直写喷头4和墨水储备罐5运动或静止。
将原料1.0wt%引发剂(Irgacure 784),1.0wt%NaYF4上转换纳米粒子,13.0wt%触变剂(气硅,赢创TS100),42.5wt%环氧丙烯酸酯树脂及42.5wt%单体丙烯酸三羟甲基丙烷酯(TMPTA)称量后在混料消泡机种充分混合得到墨水(弹性模量G’为0.53kPa,损耗模量G”为0.28kPa)。将墨水装填至墨水储备罐中,控制挤出压力为50kPA,墨水通过直写喷头(0.21,0.41,0.80,1.55,2.50,4.00mm)被挤出,直写喷头通过控制器在水平面内做往复运动,激光发射结构与直写喷头呈相对静止,光束位于直写喷头正下方2mm处。激光发射结构发射出波长为980nm的光束,激光功率为3.5W,打印速度控制为1.0mm/s。可得到不同线宽的线条,如图2所示。通过全反射傅里叶变换红外光谱测定特征吸收峰变化,无论线径变宽(0.41-4.00mm),转化率并无明显波动,在50%左右,证明利用近红外穿透性可以达到均匀固化。
实施例2:
利用近红外光实时固化:采用实施例1中墨水相同工艺参数、直写打印设备及其工作参数,仅使用0.41mm喷头进行网格打印(先控制直写喷头在水平面内做往复运动,然后控制直写喷头上抬并改变原运动方向继续进行往复运动),得到如图3右所示的3D打印物件。
对利用近红外光在打印后固化:采用上述相同的墨水工艺参数、直写打印设备及其工作参数,使用0.41mm喷头进行网格打印,墨水随直写喷头移动并在挤出,得到形体,并在结束挤出后利用近红外光进行固化,得到如图3左所示的3D打印物件。
对利用近红外光在打印后固化及利用近红外光实时固化进行对比,如图2所示。后固化样品线条出现塌陷,而实时固化样品线条保持较佳,结构规整。
实施例3
近红外光聚合的墨水直写三维打印设备工作设置同实施例1.,将1.0%wt引发剂(Irgacure784),1.0wt%NaYF4:Yb,Tm上转换纳米粒子,0.5wt%色浆(红,黄,蓝,白),12.5wt%触变剂(气硅,赢创TS100),42.5wt%环氧丙烯酸酯树脂及42.5wt%单体丙烯酸三羟甲基丙烷酯(TMPTA)称量后在混料消泡机种充分混合得到墨水(弹性模量G’为0.49kPa,损耗模量G”为0.25kPa)。将墨水装填至打印机中,控制挤出压力为50kPA,使用1.55mm直写喷头,激光功率为3.5W,打印速度控制为1.0mm/s。可得到不同颜色的线条,结果如图4所示。如图5所示,根据紫外-可见光吸收光谱,所用引发剂的吸收波段(300-500nm)与色浆的吸收峰重叠,在吸收并利用光源能量过程中存在竞争关系,若使用紫外-蓝光进行打印固化难以实现固化。通过全反射傅里叶变换红外光谱测定近红外固化后样品特征吸收峰变化,不同颜色相转化率并无明显波动,在40%左右,证明利用近红外穿透性可以实现彩色样品固化。
实施例4
将实施例3中的色浆在相同工艺下使用同轴喷头(1.3mm外,0.5mm内)进行同时双色彩挤出:使用同轴喷头(1.3mm外,0.5mm内)作为直写喷头,同时装填两种色彩墨水连接至同轴喷头内外流道,在作用力下挤出同时受到近红外的照射,实现固化得到具有内外具有两种色彩的线条。证明利用近红外穿透性实现多色彩/多材料的可能性,结果如图6所示。
实施例5
在实施例3中的打印参数下,通过同时抬升直写喷头以及近红外光斑,使墨水由基材逐渐向悬空中挤出并固化,可实现3D打印自支撑的悬空结构。相对于传统3D打印方法,例如热固化的墨水直写,立体光刻等技术需要在悬空结构上增加额外支撑并在打印后进行裁切。本方法利用近红外固化的穿透性和可控性促使墨水快速均匀达到凝胶点实现自支撑的能力。
Claims (10)
1.一种基于近红外光聚合的墨水直写三维打印的方法,其特征在于,所述方法为:直写喷头在三维空间中运动或静止,墨水从直写喷头中被挤出,在接受近红外光的照射,固化后完成三维物体成型,并且固化时间t不超过近红外光直径dl与墨水挤出速度vi比值,即t≤dl/vi。
2.根据权利要求1所述的一种基于近红外光聚合的墨水直写三维打印的方法,其特征在于,所述直写喷头的运动速度为0~5.0mm/s,所述直写喷头的直径范围为0.1μm~10㎝。
3.根据权利要求1所述的一种基于近红外光聚合的墨水直写三维打印的方法,其特征在于,所述墨水的组成包括可光聚合树脂、可光聚合单体、光引发剂、上转换材料、触变剂、填料。
4.根据权利要求1所述的一种基于近红外光聚合的墨水直写三维打印的方法,其特征在于,所述墨水的流变性能要满足以下条件:
弹性模量G’为损耗模量G”的0.5~5倍,即0.5G”≤G’≤5G”。
5.根据权利要求1所述的一种基于近红外光聚合的墨水直写三维打印的方法,其特征在于,所述挤出墨水的作用力为压力,所述压力不超过800kPa。
6.根据权利要求1所述的一种基于近红外光聚合的墨水直写三维打印的方法,其特征在于,所述近红外光为光束或光斑,并且光斑或光束位于直写喷头1厘米空间内。
7.根据权利要求1或6所述的一种基于近红外光聚合的墨水直写三维打印的方法,其特征在于,所述近红外光的功率为0-50W,波段范围为700-2000nm。
8.根据权利要求3所述的一种基于近红外光聚合的墨水直写三维打印的方法,其特征在于,所述可光聚合树脂包括含丙烯酸酯双键的树脂、含乙烯基醚双键的树脂、含环氧基团的树脂,优选为含丙烯酸酯双键的树脂;
可光聚合单体包括单官能丙烯酸酯类单体、双官丙烯酸酯类单体、多官能丙烯酸酯类单体、乙烯基醚类单体、酯环族环氧类单体、氧杂环丁烷类单体中的一种或多种;
光引发剂包括2,4,6-三甲基苯甲酰二苯基氧化膦、1-羟基环己基苯基甲酮、2,4,6-三甲基苯甲酰基苯基膦酸乙酯、双2,6-二氟-3-吡咯苯基二茂钛、苯基双(2,4,6-三甲基苯甲酰基)氧化膦、2-异丙基硫杂蒽酮、2-羟基-2-甲基-1-苯基丙酮、2-甲基-2-(4-吗啉基苯基)-1-[4-(甲硫基)苯基]-1-丙酮、1,7,7'-三甲基-双环(2,2,1)庚烷-1,3-二酮、四氟硼酸甲基二苯基硫鎓盐、4,4'-二甲基二苯基碘鎓盐六氟磷酸盐、二茂铁类六氟磷酸盐中的一种或多种;
上转换材料包括NaYF4、BaYF5、NaGdF4、LiYF4、NaYbF4、Na3ScF6、YF3、GdOF中的一种或多种;
触变剂包括气硅;
填料包括硫酸钡、钛白粉、二氧化硅、滑石粉中的一种或多种。
9.根据权利要求3或8所述的一种基于近红外光聚合的墨水直写三维打印的方法,其特征在于,所述墨水中含有颜料。
10.一种基于近红外光聚合的墨水直写三维打印的装置,其特征在于,所述设备包括:
支撑台,用于支撑成型的三维物体;
近红外光发射结构位于支撑台上方,与控制器固定连接,控制器驱动近红外光发射结构运动或静止;
直写喷头位于支撑台上方,直写喷头与墨水储备罐密封连接,直写喷头和/或墨水储备罐与控制器固定连接,控制器驱动直写喷头和墨水储备罐运动或静止。
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