CN107548346A - 通过气溶胶的飞行中固化制造三维结构 - Google Patents

通过气溶胶的飞行中固化制造三维结构 Download PDF

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CN107548346A
CN107548346A CN201680020145.5A CN201680020145A CN107548346A CN 107548346 A CN107548346 A CN 107548346A CN 201680020145 A CN201680020145 A CN 201680020145A CN 107548346 A CN107548346 A CN 107548346A
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迈克尔·J·雷恩
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Abstract

一种用于制造三维结构的方法。飞行中加热或UV照射在气溶胶滴被喷射到目标表面上时改变所述气溶胶滴的性质。UV光至少部分地将光聚合物滴固化，或者备选地造成基于溶剂的纳米颗粒分散体的微滴在飞行中快速地干燥，并且导致的气溶胶滴增加的粘度促进独立式三维结构的形成。该3D制造可以使用各种各样的光聚合物、纳米颗粒分散体和复合材料进行。得到的3D形状可以是独立式的，没用支撑体的情况下制造的，并且可以通过相对于目标衬底操作打印喷嘴获得任意形状。

Description

通过气溶胶的飞行中固化制造三维结构
相关申请的交叉引用
本申请要求2015年2月10日提交的名称为“微3D打印”的美国临时专利申请序列号62/114,354的优先权和提交利益，并且其说明书和权利要求通过引用并入本文。
发明背景
发明领域(技术领域)
本发明涉及通过气溶胶喷射的纳米颗粒和聚合物墨水的飞行中固化制造3D电气和机械结构、微结构和纳米结构。
背景技术
注意，以下讨论可以参考大量的出版物和参考文献。本文中这种出版物的讨论被给出用于科学原理的更完整背景，而不被解释为承认这种出版物是用于可专利性确定目的的现有技术。
三维打印是迅速进展的技术，其有希望引起增材制造革命。利用3D打印，多种结构材料如塑料盒金属可以制造成网状结构而不需要减材加工或刻蚀步骤。几乎不存在材料浪费，并且减少的加工步骤有希望使3D打印成为成本效益好的绿色技术。现今，数种3D打印技术是当前可用的，并且简要地将这些技术与本发明进行比较是有用的。
立体平版印刷术是一种增材制造工艺，其通过将紫外(UV)激光聚焦到一桶光聚合物树脂上工作。在计算机辅助制造或计算机辅助设计(CAM/CAD)软件的帮助下，使用UV激光将预先程序化的设计或形状刻画到光聚合物桶的表面上。因为光聚合物在紫外光下是光敏的，所以照射的树脂凝固并且形成单层的所需3D物体。对于设计的每层重复该过程直到3D物体完整。50-150um的层分辨率一般伴随接近10um的横向尺寸。该过程通常限于光聚合物材料，并且需要牺牲结构支撑悬伸物。
喷墨技术一般用于以2D方式打印石墨和颜料墨水。近期的材料创新使得喷墨打印机能够喷射聚合物和金属纳米颗粒墨水。通常，喷墨打印中使用的墨水必须具有较低的粘度，意味着墨水在打印后将会充分地铺展，从而限制所打印的特征的最小特征尺寸和高宽比。喷墨器不接触衬底，但是其非常接近(小于mm)。
挤出技术对于热塑性聚合物的3D打印是普遍的。在该情况下，将热塑料在喷嘴中加热至熔融点并挤出到衬底上。塑料在接触衬底时快速冷却和凝固，并且可以维持三维形状。3D部件一般逐层制造，每层都由挤出丝线的线栅图样构成。悬伸物可以通过挤出牺牲性支撑材料和之后的溶解或机械地移除支撑结构来制造。一般地，特征尺寸是几百微米，并且材料很大程度限于热塑性塑料和少数热固性聚合物以及导电浆料。nScrypt工具能够通过对喷嘴定位的自动的CAD/CAM控制来在3D表面上打印。
发明概述(发明内容)
本发明是用于在衬底上制造三维结构的方法，所述方法包括将气溶胶滴从沉积头朝向所述衬底推进，在飞行中部分地改变所述气溶胶滴的性质，以及在所述气溶胶滴已经沉积作为所述三维结构的一部分后，完全地改变所述气溶胶滴的所述性质。改变性质任选地包括使用电磁辐射固化，例如紫外(UV)光固化，或者凝固。在该实施方案中，气溶胶滴优选地包含可光固化的聚合物，并且所制造的三维结构包含固化的聚合物。所述气溶胶滴任选地包含分散于所述可光固化的聚合物中的固体颗粒，并且所制造的三维结构包含固化的聚合物，所述固化的聚合物包含包埋的固体颗粒。所述固体颗粒任选地包括陶瓷、金属、纤维或硅。在另一实施方案中，所述气溶胶滴包含溶剂，并且改变性质包括蒸发所述溶剂。这些气溶胶滴任选地包含金属纳米颗粒，在这种情况下所述方法优选地还包括用UV辐射照射所述气溶胶滴，加热所述金属纳米颗粒，以及充分加热所述气溶胶滴以至少部分地蒸发所述溶剂。所述方法优选地还包括在所述金属纳米颗粒已经沉积后继续照射所述金属纳米颗粒，由此至少部分地烧结所述金属纳米颗粒。
所述方法任选地包括使所述沉积头相对于所述衬底倾斜或平移。所述方法任选地包括在不需要牺牲性支撑体或者倾斜所述沉积头或所述衬底的情况下制造悬伸的结构。所述沉积头和所述衬底之间的相隔距离优选为至少1mm，并且更优选至少2mm。所述方法优选地包括在飞行中增加所述气溶胶滴的粘度，并且优选地包括在飞行中和在所述气溶胶滴已经沉积后用电磁辐射照射所述气溶胶滴，任选地在飞行中从多于一个方向。所述方法任选地包括在飞行中和在所述气溶胶滴已经沉积后用电磁辐射加热所述气溶胶滴。所制造的三维结构任选地包括选自由以下各项组成的组中的结构：微米尺寸表面纹理、机械插入物(mechanical interposer)、精确间隔物、包含包埋的电连接器的机械插入物、封闭的中空结构、机械支架(scaffold)和功能性电线。
本发明的目的/优点和新特征以及实用性的其他范围将结合附图在以下详细描述中部分地阐明，并且在查阅以下内容后对于本领域技术人员将部分地变得明显，或者可以通过本发明的实践学习。本发明的目的和优点可以凭借所附权利要求中具体指出的手段和组合而实现和获得。
附图简述
并入到说明书并形成说明书一部分的附图说明本发明的数个实施方案，并连同说明书用于解释本发明的原理。附图仅为了说明本发明的优选实施方案，而不解释为限制本发明。在附图中：
图1是说明利用气溶胶射流三维打印的机理的示意图。
图2A-2C是根据本发明的一个实施方案打印的聚合物柱的阵列的图像。图2D是示出柱构建速率的图表。
图3是复合材料柱的阵列的图像。
图4A和4B分别是根据本发明的一个实施方案打印的插入物的立体图和顶视图。
图5A示出使用图1中所示的偏移法打印的三维千斤顶状(jack-like)结构。图5B示出开口锥体结构。
图6A和6B示出具有沿长度的开放内部的闭合通道。图6C示出在通道的内侧流动的墨水。
图7A和7B分别示出具有L形打印柱的单个天线和天线的阵列。图7C和7D是在微芯片上打印的3D电气部件的图像。
图8A示出通过在打印期间倾斜打印头制造的独立式聚合物弹簧。图8B示出支撑质量的弹簧。
图9A是示出银纳米颗粒的光密度的图表。图9B示出利用原位照射法打印的3D银线阵列。
图10A-10F是使用UV聚合物和飞行中固化打印的多种3D形状的图像。
发明的实施方案的详述
本发明是制作三维结构如包括高高宽比特征的结构的方法，其使用气溶胶和墨水的飞行中固化和液体材料的直接打印制造三维独立式复杂结构。具体地，本发明的实施方案将获得专利的Aerosol Jet分散技术，如美国专利第7,674,671、7,938,079和7,987,813中描述的技术，与使得液滴能够在沉积在表面上前部分地凝固的飞行中材料加工机理组合。在飞行中加工后，微滴可以沉积以形成独立式结构。该方法的一部分优点包括超高分辨率三维(3D)打印，具有低至10微米的特征尺寸、达1微米的横向特征分辨率、和达100nm的垂直分辨率。独立式结构的高宽比可以大于100，并且结构可以通过操作打印头相对于那些表面的倾斜和位置打印在几乎任何表面和表面几何形状上。可以直接打印悬伸物和闭合的室，而无需使用牺牲性支撑材料。可以加工金属和绝缘材料两者，这使得用于制造电路的电子材料能够以3D的方式共沉积。此外，可以打印复合材料，这允许调整3D结构的力学和电学性质。紫外(UV)聚合物可以在它们影响目标时在飞行中固化，而且低的烧结温度使得塑料能够金属化。使用Aerosol Jet工艺，实际上可以打印任何类型的材料和/或溶剂。对于该工艺来说，与衬底大的间隔(一般几毫米)使得能够高高宽比打印而无需任何z轴移动。气溶胶射流的低于10微米聚焦使得能够建立超精细特征。
Aerosol Jet打印是非接触的基于气溶胶的喷射技术。起始墨水配制为具有低粘度(0.5至1000cP)，并且在一般工艺中它们首先雾化成1-5um直径微滴的细微滴分散体。优选地，氮气带走微滴并且推进它们穿过细喷嘴(0.1-1mm内径)到用于沉积的目标衬底。同向流动，优选氮鞘气体使微滴射流聚焦低至10um直径，这允许打印该尺寸的特征。喷射技术以喷嘴和衬底之间大的相隔距离(几mm)、高分辨率(特征宽度10um)、体积分散准确度(10飞升(femptoliter))和宽范围的材料相容性而著称。由于大的相隔距离，在微滴飞行至衬底期间将微滴干燥和/或否则固化是可能的。在这样做时，微滴的粘度可以增加到远超过起始粘度。由于较高的粘度，打印的墨水是自支撑的，并且可以被构建成独立式柱和其他高高宽比特征。为了增加粘度，优选地将来自灯或UV LED的UV光施加到喷嘴出口和目标衬底之间的间隙区域，如图1中所示。如果起始墨水包含具有与UV发射光谱重叠的吸收带的光聚合物，则UV光可以在飞行中完全地或者部分地固化光聚合物滴，从而增加粘度。
图1是说明利用气溶胶射流三维打印的机理的示意图。微3D结构优选通过使用Aerosol Jet相容的低粘度可光固化树脂制造，其优选地使用Aerosol Jet技术打印。电磁辐射，在该情况下为紫外光，照射并且在飞行途中部分地固化微滴。部分固化增加微滴的粘度，这进而限制沉积物在衬底上的铺展。微滴在目标衬底上合并，然后完全固化。上示意图示出垂直堆叠的微滴。下示意图示出当衬底在打印头下方平移时构建悬伸结构的微滴。已经验证了高达45度的悬伸物，尽管可以实现甚至更大的角度。
图2A是利用Loctite 3104丙烯酸氨基甲酸酯和同时的UV LED固化打印的垂直聚合物柱的照片。入射UV功率是0.65mW，UV波长是385nm，并且体积打印速率是7.5nL/s。柱可以从目标衬底基本上延伸至气溶胶喷射喷嘴出口。图2B是柱阵列的放大图像；柱高度是1.0mm，高度变化率是1％，间隔是0.5mm，并且直径是90μm。图2C是柱阵列的上表面的图像。每个柱的顶部都具有圆形的几乎半球状的形状。图2D是示出所测量的单柱建造速率的图表。发现当打印喷嘴在给定位置固定时，柱高度与时间成比例。高度的变化率是约1％，或者备选地对于1.0mm高的柱是约10μm。
当固体颗粒如陶瓷、金属或纤维分散于光聚合物墨水中时，飞行中加工也是可能的。在该情况下，固化的光聚合物用作用于固体颗粒的3D机械支撑体。该复合材料的力学和电学性质可以通过例如提供耐磨损性以及形成3D导电体来优化。图3是复合材料柱的阵列的图像。将具有小于500nm的粒度的硅粉以7体积％的浓度分散于UV光聚合物树脂中。然后将复合分散体打印并且在飞行中固化以产生具有包埋的硅的固化的树脂的固体柱。柱直径是120μm，并且高度是1.1mm。复合材料对于优化3D结构的力学和电学性质是理想的。在该实例中，组合物材料对UV光是充分透明的，使得其甚至利用单侧UV照射也完全固化。在更大的浓度和在高吸收颗粒的情况下，复合树脂可能对入射光不透明。在该情况下，可能必须从相反的侧面照射打印区域，或者用环形灯照射沉积物。只要UV树脂在3D结构的外表面附近固化，充足的机械支撑体就会允许垂直地构建结构。可以任选地在后处理步骤中移除光聚合物，如通过将3D结构加热至超过光聚合物的蒸发或分解点。
图4示出打印的机械插入物的图像，所述机械插入物是提供两个分开的部件之间的结构支撑和精确间隔的元件。通过堆叠多层UV树脂打印插入物，如在图4A的立体图中可以看到的。图4B示出上表面网格图样。在一些实施方案中，插入物可以提供一个元件与另一个之间的电气或流体线路或到另一个的连接，在这种情况下间隙空间可以用导电材料或流体填充。
图5A示出使用图1中所示的偏移法打印的三维千斤顶状结构。下部4条腿在使打印头沿x-和y-方向平移至顶点的同时打印。有角度的柱是相对于衬底约45度角。顶部腿通过使打印头平移远离顶点打印。总体高度是4mm，并且单个柱直径是60μm。图5B示出开口锥体结构。这通过使工作台以具有增加半径的重复环形移动平移来打印。如果需要，锥体可以通过继续环形移动并且减小半径至零来闭合。
图6A和6B示出具有沿长度的开放内部的闭合通道。通道的每个侧壁都通过堆叠可光固化的聚合物的线并且循序地偏移约1/2的线宽来打印。该过程导致在偏移方向以约45度倾斜的壁。通过以相反方向偏移，壁在中点处接触。图6C描绘布置在通道入口附近的有色墨水滴，看到所述有色墨水滴被表面张力拉动穿过通道。这验证了通道沿长度是封闭的但是通道从端到端是完全开放的。
图7A示出用作电子元件的机械支撑体的光固化柱。聚合物柱使用图1中的工艺制造，并且其是大约1mm高乘以0.1mm宽。银墨水通过使打印头以相对于每个45度倾斜打印到柱和衬底的侧壁上。银墨水在打印期间具有低粘度，并且因此将在衬底上稍微铺展。通过提供机械支撑体，银墨水可以沿着支撑体的表面以三维方式打印。在打印后，将银墨水在箱式烘炉中在150℃热烧结60分钟。得到的导电图样用作独立式毫米波偶极天线。图7B示出微天线的阵列。图7C和7D是在微芯片上打印的3D电气部件的图像。本发明的方法消除了否则将不得不构建到包装中的复杂的连接和波导。该实例表明，功能装置如3D电子元件(例如加热器、天线和互相连接)可以直接打印在驱动器芯片上。
图8A示出通过在打印期间倾斜打印头制造的独立式聚合物弹簧。打印头在每个弹簧的构建期间从0°倾斜至-30°并回到0°。图8B描绘表明弹簧阵列可以支撑力学质量的验证。与前述垂直柱相比，弹簧提供在两个表面之间的挠性插入物连接。
在基于溶剂的墨水如金属纳米颗粒分散体的情况下，微滴粘度可以通过在飞行期间部分地或完全地干燥微滴而增加。由于已知金属纳米颗粒对UV光高度吸收，因此将微滴暴露于UV照射将加热纳米颗粒并加速溶剂蒸发。图9示出这种将原位固化工艺扩展至非可光固化材料。图9A是示出随着粒度减小银纳米颗粒在UV波长增加的光密度(即吸收光谱)的图表。曲线在410nm附近具有强峰，但是吸收边延伸到可见光，使得飞行中加工可能利用常用的UV LED和汞灯。包含分散于溶剂中的银纳米颗粒的墨水滴由此可以通过吸收在400nm附近波长的UV光得到加热。如果在飞行中受热，则溶剂将会大量蒸发，并且在银滴影响表面时导致高度浓缩的银滴。金属纳米颗粒滴可以保持它们的3D形状，既因为载体溶剂被蒸发，也因为颗粒被部分地烧结。现在，更高粘度的银滴可以以3D方式堆叠，类似于光聚合物的堆叠。将纳米颗粒加热到超过蒸发溶剂所需水平的打印后的进一步照射将使纳米颗粒至少部分地烧结并变得导电。图9B示出利用原位照射法打印的3D银线阵列。线宽度是40μm，并且高度是0.8mm。线由于以下事实稍微弯曲：仅使用单侧照射，这造成线在照射侧被加热得更多，导致不对称收缩。
图10A-10F是使用UV聚合物和飞行中固化打印的多种3D形状的图像。图10A示出柱状物(0.1mm间距，0.25mm高)。图10B示出扭曲的片状物(0.5mm宽，2mm高)。图10C示出箱状物(1mm长，0.25mm高，0.03mm壁)。图10D示出帽状物(0.5mm直径，0.5mm高)。图10E示出锥体(0.5mm直径，0.5mm高)。图10F示出泡状物(0.5mm直径，1mm高)。
在本发明的实施方案中，UV照射正用于在气溶胶滴被喷射到目标表面上时改变所述气溶胶滴的性质。具体地，UV光至少部分地固化光聚合物滴，并且导致的增加的粘度促进独立式结构的形成。UV光备选地造成基于溶剂的纳米颗粒分散体的微滴在飞行中快速地干燥，同样地实现3D制造。该3D制造可以使用各种各样的光聚合物、纳米颗粒分散体和复合材料进行。得到的3D形状可以是独立式的，没用支撑体，并且可以通过相对于目标衬底操作打印喷嘴获得任意形状。特征尺寸主要通过喷射工艺确定，并且可以低至10μm或甚至更低。
尽管已经具体参照所公开的实施方案详细说明了本发明，但是其他实施方案可以实现相同的结果。本发明的变化和改变对于本领域技术人员将会是明显的，并且意图涵盖全部这些改变和等同方案。以上引用的所有专利和出版物的完整公开内容都通过引用并入本文。

Claims (18)

1.一种用于在衬底上制造三维结构的方法，所述方法包括：
将气溶胶滴从沉积头朝向所述衬底推进；
在飞行中部分地改变所述气溶胶滴的性质；以及
在所述气溶胶滴已经沉积作为所述三维结构的一部分后，完全地改变所述气溶胶滴的所述性质。
2.根据权利要求1所述的方法，其中改变性质包括使用电磁辐射固化或凝固。
3.根据权利要求2所述的方法，其中固化包括紫外(UV)光固化。
4.根据权利要求2所述的方法，其中所述气溶胶滴包含可光固化的聚合物，并且所制造的三维结构包含固化的聚合物。
5.根据权利要求4所述的方法，其中所述气溶胶滴包含分散于所述可光固化的聚合物中的固体颗粒，并且所制造的三维结构包含固化的聚合物，所述固化的聚合物包含包埋的固体颗粒。
6.根据权利要求5所述的方法，其中所述固体颗粒包括陶瓷、金属、纤维或硅。
7.根据权利要求1所述的方法，其中所述气溶胶滴包含溶剂，并且改变性质包括蒸发所述溶剂。
8.根据权利要求7所述的方法，其中所述气溶胶滴包含金属纳米颗粒，所述方法还包括：
用UV辐射照射所述气溶胶滴；
加热所述金属纳米颗粒；以及
充分加热所述气溶胶滴以至少部分地蒸发所述溶剂。
9.根据权利要求8所述的方法，所述方法还包括在所述金属纳米颗粒已经沉积后继续照射所述金属纳米颗粒，由此至少部分地烧结所述金属纳米颗粒。
10.根据权利要求1所述的方法，所述方法还包括使所述沉积头相对于所述衬底倾斜或平移。
11.根据权利要求1所述的方法，所述方法包括在不需要牺牲性支撑体或者倾斜所述沉积头或所述衬底的情况下制造悬伸的结构。
12.根据权利要求1所述的方法，其中所述沉积头和所述衬底之间的相隔距离是至少1mm。
13.根据权利要求12所述的方法，其中所述沉积头和所述衬底之间的相隔距离是至少2mm。
14.根据权利要求1所述的方法，所述方法包括在飞行中增加所述气溶胶滴的粘度。
15.根据权利要求1所述的方法，所述方法包括在飞行中和在所述气溶胶滴已经沉积后用电磁辐射照射所述气溶胶滴。
16.根据权利要求15所述的方法，所述方法包括在飞行中从多于一个方向用电磁辐射照射所述气溶胶滴。
17.根据权利要求1所述的方法，所述方法包括在飞行中和在所述气溶胶滴已经沉积后用电磁辐射加热所述气溶胶滴。
18.根据权利要求1所述的方法，其中所制造的三维结构包括选自由以下各项组成的组中的结构：微米尺寸表面纹理、机械插入物、精确间隔物、包含包埋的电连接器的机械插入物、封闭的中空结构、机械支架和功能性电线。
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