CN109320248A - 用于陶瓷折纸结构四维打印的系统和方法 - Google Patents

用于陶瓷折纸结构四维打印的系统和方法 Download PDF

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CN109320248A
CN109320248A CN201810852295.3A CN201810852295A CN109320248A CN 109320248 A CN109320248 A CN 109320248A CN 201810852295 A CN201810852295 A CN 201810852295A CN 109320248 A CN109320248 A CN 109320248A
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printing
particle
ceramic
method described
polymer
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CN109320248B (zh
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吕坚
刘果
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City University of Hong Kong CityU
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Abstract

本发明公开了一种构造4D打印的陶瓷物体的系统和方法，包括：通过喷嘴挤出包括颗粒和陶瓷前驱体的墨水，以将墨水沉积在加热板上，由此在加热板上形成3D打印的弹性物体；将3D打印的弹性物体折叠成复杂结构以形成4D打印的预应变弹性物体；以及将4D打印的弹性物体转换成4D打印的陶瓷物体。

Description

用于陶瓷折纸结构四维打印的系统和方法
技术领域
本发明涉及陶瓷结构的打印。具体地说，本发明的实施例涉及使用高分子化合物打印可折叠物体。折纸的具体实施例以这样的方式打印，使得物体的折叠凭借材料特性而发生。
背景技术
在本说明书中，应该理解，术语“折纸”是指将薄片折叠成三维(3D)物体的过程。
在制造和3D打印的环境中，提及“折纸”装配是指使3D打印物体“折叠”成更复杂形状的过程。
这种折叠可以通过毛细作用力、通过使用机械感应器、或通过形成3D打印物体的材料固有的形状记忆机构来发生。
在口语中，类似折纸的3D打印物体(即，通过其固有结构和/或材料的使用而能够随时间移动或变形的物体)通常通过称为四维(4D)打印的过程而制造。因此，在本说明书的上下文中，将理解的是，对“4D打印物体”的任何引用是对使用3D打印技术打印的物体的引用，但是由于物体的固有属性，其能够随时间变换。相应地，4D打印是指采用3D打印机构或方法的打印过程，并且在某些情况下，在进行形状变形步骤之前，采用产生4D打印物体的方式。
可以理解的是，4D打印物体和4D打印技术可以应用在包括机器人技术、生命科学应用和仿生4D打印等的多个领域中。
通过陶瓷前驱体的热分解制备的聚合物衍生陶瓷(PDCs)除了机械抗摩擦学性能外，还表现出常规陶瓷的显著性能，例如高热稳定性、耐氧化和耐腐蚀的化学特性。PDCs的微观结构和性质可以通过调节聚合物体系和热解条件进行调整。
陶瓷前驱体的增材制造是用于构建复杂陶瓷结构的最先进的技术。但是，硅树脂在用于聚合物向陶瓷转化的完全交联后不够柔软，很难弯曲。
正是在这种背景下开发了本发明。
发明内容
在一个方面，本发明提供一种构造4D打印的陶瓷物体的方法，所述方法包括：通过喷嘴挤出包括颗粒和陶瓷前驱体的墨水，以将墨水沉积在加热板上，由此在加热板上形成3D打印的弹性物体；将3D打印的弹性物体折叠成复杂结构以形成4D打印的预应变弹性物体；以及将4D打印的弹性物体转换成4D打印的陶瓷物体。
在一个实施方式中，颗粒是二氧化锆纳米颗粒。
在一个实施方式中，陶瓷前驱体是聚二甲基硅氧烷。
在一个实施方式中，加热板的温度在约30℃至约400℃的范围内。
在一个实施方式中，弹性物体的折叠通过金属线来实现。
在一个实施方式中，聚合物向陶瓷转化通过在真空中或在惰性气氛下热解发生。
在一个实施方式中，4D打印的陶瓷物体具有混合的高斯曲率。
该混合的高斯曲率可以是有利的，因为弹性体的拉伸性提供了构建复杂结构的机会。
在一个实施方式中，4D打印的陶瓷物体具有100μm或更大的尺寸。
在一个实施方式中，墨水由颗粒在陶瓷前驱体中均匀分布形成，并且其中，墨水中颗粒的重量百分比在约1％至约90％的范围内，以及墨水中陶瓷前驱体的重量百分比在约10％至约99％的范围内。
在一个实施方式中，聚合物向陶瓷转化的加热温度为400℃至2000℃。
在一个实施方式中，聚合物结构在所述聚合物向陶瓷转化期间经历有限且均匀的收缩，并且其中，4D打印的陶瓷物体具有与4D打印的弹性物体基本相同的形状。
在一个实施方式中，颗粒的特征在于约100μm或更小的平均直径。
在一个实施方式中，颗粒是均匀分布的粉末。
在一个实施方式中，弹性物体被局部或部分加热以实现所述陶瓷-有机结构。
在一个实施方式中，通过使用以下中的至少一者实现弹性物体的折叠：金属线、预拉伸装置、金属板、聚合物线、聚合物板、碳线、碳板、硅线、硅板、形状记忆合金和形状记忆聚合物。
在一个实施方式中，陶瓷前驱体包括以下几者中的至少一种：聚硅氧烷、聚倍半硅氧烷、聚碳硅氧烷、聚碳硅烷、聚硅烷基碳二亚胺、聚倍半硅烷基碳二亚胺、聚硅氮烷和聚倍半硅氮烷。
在一个实施方式中，颗粒包括以下几者中的至少一种：二氧化锆颗粒、氧化钙颗粒、氧化铝颗粒、二氧化钛颗粒、氧化铟颗粒、氧化锌颗粒、二氧化硅颗粒、氮化铝颗粒、硅酸钙颗粒、碳化硅颗粒、聚合物颗粒、金属颗粒、炭黑颗粒、石墨烯颗粒、石墨颗粒、金刚石颗粒和耐火材料。
在一个实施方式中，在聚合物向陶瓷转化的过程中，预应变通过机器人或形状记忆合金或热膨胀或弛豫残余应力或激光切割韧带或其组合来预调。
附图说明
尽管任何其他形式可以落入本发明范围内，但是现在将参照附图仅以举例的方式描述优选实施例，其中：
图1示出了根据本发明的实施例的DIW-折纸-SCOP方法，其中a部分示出了用于折纸的3D打印的弹性体晶格；b部分示出了DIW方法的示意图；c部分示出将3D打印的弹性体转化成预应变前驱体的金属丝辅助折纸步骤；部分d示出将预应变前驱体热解转化成4D打印陶瓷的步骤；e部分示出了在销蚀掉金属线之后获得的一级PDCs；f部分示出了将一级PDCs转化成二级PDCs的氧化步骤；
图2示出了3D打印的大尺度弹性蜂窝体的实例；
图3显示了3D打印的PDMS纳米复合材料的微晶格(部分(a))和蜂窝(部分(b))，一级PDCs和二级PDCs(从左到右)的例子；
图4显示了二级PDCs的多级纳米结构的一个例子：微晶格的数码照片(部分a；比例尺，5mm)，微晶格的SEM图像(部分b；比例尺，200μm)，横截面的SEM图像(部分c；比例尺，100nm)和孔径分布(部分d)，部分e显示了这种多级陶瓷纳米结构的相关尺寸的示意图；
图5例示了PDCs的孔隙率(部分a)，一级和二级PDCs的N2吸附/解吸等温线(部分b)，其中，部分b中的插图示出了一级和二级PDCs的累积孔体积和孔径分布；
图6显示了通过弯曲、扭转和拉伸呈现的打印弹性体的柔性和拉伸性；
图7展示了模仿蝴蝶、悉尼歌剧院、玫瑰和裙子的代表性陶瓷折纸物体；
图8显示了大尺度4D打印陶瓷；
图9显示了通过DIW-折纸-SCOP方法产生具有混合的高斯曲率(K)的复杂4D打印陶瓷，其中，a和d部分显示在4D打印陶瓷中的正K(球形帽)和零K(圆柱体)，b部分显示4D打印陶瓷中的正K(环面的外部区域)和负K(环面的内部区域)，以及c部分表示4D打印陶瓷中的零K(圆锥和圆柱体)；
图10显示了抗压强度-密度的Ashby图。对比了本发明中具有高抗压强度的SiOC基质纳米复合材料结构(红色星号)与参考文献报道的和市售SiC泡沫和AlSiO泡沫的其他陶瓷结构；
图11显示了强度-尺度的协同作用。同时具有高强度和大尺度的PDCs结构；以及
图12A、图12B、图12C和图12D是表1中相关条目的示例性几何表示的图示。
具体实施方式
在随后的描述中，为了简洁起见、为了提高可读性，某些术语一旦引入将被缩写。应该理解的是，这些缩写的使用不应该被解释为限制性的或以其他方式对这些术语的含义赋予超出本领域技术人员所理解的含义的“光泽”。
在至少一个实施方案中，本发明提供了构建4D打印陶瓷物体的方法，所述方法包括：挤出含有颗粒的墨水；陶瓷前驱体，通过喷嘴将墨水沉积在加热板上，由此在加热板上形成3D打印的弹性物体，将3D打印的弹性物体折叠成复杂的折纸或剪纸结构，从而形成4D打印预应变弹性物体；以及将4D打印的弹性物体转换成4D打印的陶瓷物体，由此形成4D打印的陶瓷物体。
更详细地说，所用的硅橡胶纳米复合材料(NCs)是用ZrO2纳米颗粒(NPs)填充的聚二甲基硅氧烷(PDMS)。
PDMS是有机硅系统中的主要弹性体，可用作陶瓷前驱体，同时提供固有的柔性，以构建适用于折纸折叠的材料。此外，PDMS的可拉伸性允许创建具有混合高斯曲率的精美折纸结构。该结构可以具有正高斯曲率、负高斯曲率、零高斯曲率或其组合。
在参照附图给出的实例中，具有主要尺寸为直径20-50nm的结晶ZrO2纳米颗粒被加入到PDMS基质中，在聚合物基质内形成阻塞网络，同时作为在聚合物基质中的质量和热量传导的障碍，从而减小陶瓷化时的收缩。
优选地，聚合物向陶瓷的转化通过在惰性气氛中热解、在氧化气氛中氧化或其技术的组合来实现。
应当理解，颗粒也可以是氧化钙颗粒、氧化铝颗粒、二氧化钛颗粒、氧化铟颗粒、氧化锌颗粒、二氧化硅颗粒、氮化铝颗粒、硅酸钙颗粒、碳化硅颗粒、聚合物颗粒、金属颗粒、炭黑颗粒、石墨烯颗粒、石墨颗粒、金刚石颗粒、其它耐火材料或上述颗粒的任何组合。
在该实施例中，颗粒的特征在于平均直径为约100μm或更小，并且可以是均匀或非均匀分布的粉末或纤维或管或任何其它规则形状或上述的任何其他组合。
在这里描述的实施例中，使用了已知的节省成本的4D打印方法。该方法组合了墨水直写技术(DIW)和挤出的预聚合物墨水的同步热交联，如图1b所示。在该实施例中，墨水由颗粒在陶瓷前驱体中的均匀分布形成。在一个优选实例中，墨水中颗粒的重量百分比在约1％至约90％的范围内，并且墨水中陶瓷前驱体的重量百分比在约10％至约99％的范围内。
加热板优选在约30℃至约400℃的范围内。
3D打印的弹性体(参见图1a)与金属丝一起准备好。尽管在本文所述的实施例中使用了丝线，但将理解的是，也可以使用其他预拉伸装置。这可以包括金属板、聚合物线、聚合物板、碳线、碳板、硅线、硅板、形状记忆合金、形状记忆聚合物或上述的任何组合。
以最简单的折叠为例，陶瓷前驱体以预应变的函数被屈曲(参见图1c)。
可以理解，陶瓷前驱体可以是聚硅氧烷、聚倍半硅氧烷、聚碳硅氧烷、聚碳硅烷、聚硅烷基碳二亚胺、聚倍半硅烷基硅氧烷、聚硅氮烷、聚倍半硅氮烷或上述的任意组合。
此外，还改进了一种方法来生产被称为“热解后氧化合成陶瓷”(SCOP)的PDCs。该方法通过在氩气或真空下热解将PDMS纳米复合材料转化为SiOC基质纳米复合材料(一级PDCs)(参见图1d)，接着在空气中氧化产生二级PDCs(参见图1f)。
在聚合物向陶瓷转换后，在HNO3中销蚀掉金属线(参见图1e)，并且陶瓷的耐腐蚀性保证了在该过程期间的结构稳定性。
作为二级PDCs的前驱体，一级PDCs协助致密SiOC框架的形成。如图1所示，致密框架允许生产具有复杂曲率的4D打印的陶瓷折纸。
使用上述DIW-SCOP方法制造代表性周期结构，包括晶格和蜂窝。DIW方法的规模可扩展性由生产大尺度弹性体的蜂窝来证明(图2)。从图3中可以看出，转变中的各向同性收缩导致良好的形状保持。在1000℃氧化一级PDCs伴随着2.4％的质量损失和2.5％的线性收缩，而在1000℃下PDMS纳米复合材料的热解发生35％的质量损失和20％的线性收缩。
扫描电子显微镜(SEM)技术的使用显示样品的打印微结构(图4a)的精度是200μm(如图4b所示)，其通过喷嘴针头直径和在转化期间的收缩率确定。
在所得陶瓷晶格的横截面中，观察到直径为20-50nm的纳米颗粒(参见图4c)。良好分布着纳米颗粒的PDMS基质的降解对于一级和二级PDCs分别产生具有比表面积(Brunauer-Emmett-Teller；BET)表面积为184m2g-1和138m2g-1的多孔陶瓷(参见图5)。
PDC的孔径分布指明直径为2-10nm的超纳孔(参见图4d和图5)。与打印微结构结合的超纳多孔陶瓷可以提供高通量和期望的孔可用性，例如在陶瓷催化剂载体中。
上述陶瓷纳米结构的可编程结构层级跨越三个数量级，从200微米到10厘米(参见图4e)。
通过例如弯曲、扭转和拉伸等一些基本负载模式证明了打印弹性体的柔性和可拉伸性，为折纸装配提供了可能性(见图6)。
用3D打印的长方体或立方体预应变前驱体构建了模仿蝴蝶、悉尼歌剧院、玫瑰和裙子的具有复杂曲率的代表性陶瓷折纸结构(图7)。3D打印的弹性体晶格经历形态转变并且被金属线决定性地约束，产生4D打印的陶瓷。
弹性晶格中打印的周期性局部图案改善了整体结构的可折叠性，并保证了局部约束中的可编程性。
该方法的规模可扩展性由最大尺寸接近10厘米的弯曲陶瓷蜂窝体证明(图8)。平衡形态通过平衡弯曲和拉伸能量来确定，并且这种竞争导致依赖于厚度的平衡状态。
基于高斯定理(Gauss’s Theorema Egregium)，弹性体的可拉伸性通过改变表面上的点之间的距离，提供了构建具有混合高斯曲率的复杂结构的机会。在合成的4D打印陶瓷中产生典型的诸如圆柱体和圆锥体的零高斯曲率，类似球形帽的正高斯曲率，以及在环面的马鞍形内部区域中呈现的负高斯曲率(参见图9)。
尽管现有技术的解决方案难以直接打印具有悬空无支撑特征和混合高斯曲率的复杂结构，但本实施例的DIW-折纸-SCOP方法克服了这种限制。
此外，剪纸组装技术的应用可以结合到DIW-SCOP方法中，作为另一种强大且可定制的4D打印陶瓷方法。为了表征这些陶瓷结构的机械强度，对于一级和二级PDC，压缩测试在打印陶瓷晶格和蜂窝上进行。结果总结在图10、图11，以及表1的压缩测试样品中(下文)。
'前驱体:对于1stPDCs为PDMS纳米复合材料；对于2ndPDCs为1stPDCs
晶格表现出比蜂窝更高的比强度(强度-密度比)，并且在1.1gcm-3的晶格结构的一级PDC上获得211MPa的抗压强度。
优点和工业适用性
这里描述的实施例和更广泛的发明提供了多个优点并且具有广泛的工业实用性。
首先，作为本文中描述的实施例的一部分而被利用和开发的技术和材料允许创建具有高几何复杂度的物体，包括混合高斯曲率。
其次，所生产的物体具有较高的机械强度，比强度比传统的SiOC泡沫高约10倍。
第三，展示了强度-尺度的协同作用，这意味着本文描述的技术和材料对于工业规模的生产具有巨大的潜力。
第四，作为实施例的一部分被利用和开发的技术和材料成本低廉并且可以以成本低廉的方式打印。
第五，实施例中使用的所有材料和技术都基于市售和开放式原料系统，进一步显示了本文所述的实施方案具有商业潜力和工业实用性。
最后，从更一般的意义上讲，上述优点提供了这种可能性：实施例中的材料和技术可用于许多结构应用，包括自主变形陶瓷复合材料、航空航天推进组件和高温微机电系统。
更详细地说，作为例子，与打印微结构集成的超纳多孔陶瓷可以在例如陶瓷催化剂载体中提供高通量和期望的孔可用性。
另外，在4D打印弹性体上增加使用可编程局部加热提供了一种制造整体坚韧的陶瓷-有机结构的方法。这种基于增材制造技术的预应变弹性体衍生陶瓷折纸可用于航空航天推进、形状记忆陶瓷和生物启发的坚韧陶瓷-有机杂化材料。

Claims (18)

1.一种构造4D打印的陶瓷物体的方法，所述方法包括：
通过喷嘴挤出包括颗粒和陶瓷前驱体的墨水，以将墨水沉积在加热板上，由此在加热板上形成3D打印的弹性物体；将3D打印的弹性物体折叠成复杂结构以形成4D打印的预应变弹性物体；以及将4D打印的弹性物体转换成4D打印的陶瓷物体。
2.根据权利要求1所述的方法，其中，所述颗粒是二氧化锆纳米颗粒。
3.根据权利要求1所述的方法，其中，所述陶瓷前驱体是聚二甲基硅氧烷。
4.根据权利要求1所述的方法，其中，所述加热板的温度在约30℃至约400℃的范围内。
5.根据权利要求1所述的方法，其中，弹性物体的所述折叠通过金属线来实现。
6.根据权利要求1所述的方法，其中，聚合物向陶瓷的所述转化通过在真空中或在惰性气氛下热解发生。
7.根据权利要求1所述的方法，其中，所述4D打印的陶瓷物体可以具有混合的高斯曲率。
8.根据权利要求1所述的方法，其中，所述4D打印的陶瓷物体具有100μm或更大的尺寸。
9.根据权利要求1所述的方法，其中，所述墨水由所述颗粒在所述陶瓷前驱体中均匀分布形成，并且其中，所述墨水中所述颗粒的重量百分比在约1％至约90％的范围内，所述墨水中所述陶瓷前驱体的重量百分比在约10％至约99％的范围内。
10.根据权利要求6所述的方法，其中，聚合物向陶瓷转化的所述加热温度为400℃至2000℃。
11.根据权利要求6所述的方法，其中，所述聚合物结构在所述聚合物向陶瓷转化期间经历有限且均匀的收缩，并且其中，所述4D打印的陶瓷物体具有与所述4D打印的弹性物体基本相同的形状。
12.根据权利要求1所述的方法，其中，所述颗粒的特征在于约100μm或更小的平均直径。
13.根据权利要求1所述的方法，其中，所述颗粒是均匀分布的粉末。
14.根据权利要求1所述的方法，其中，所述弹性物体被局部或部分加热以实现所述陶瓷-有机结构。
15.根据权利要求1所述的方法，其中，通过使用以下中的至少一者实现弹性物体的所述折叠：金属线、预拉伸装置、金属板、聚合物线、聚合物板、碳线、碳板、硅线、硅板、形状记忆合金和形状记忆聚合物。
16.根据权利要求1所述的方法，其中，所述陶瓷前驱体包括以下几者中的至少一种：聚硅氧烷、聚倍半硅氧烷、聚碳硅氧烷、聚碳硅烷、聚硅烷基碳二亚胺、聚倍半硅烷基碳二亚胺、聚硅氮烷和聚倍半硅氮烷。
17.根据权利要求1所述的方法，其中，所述颗粒包括以下几者中的至少一种：二氧化锆颗粒、氧化钙颗粒、氧化铝颗粒、二氧化钛颗粒、氧化铟颗粒、氧化锌颗粒、二氧化硅颗粒、氮化铝颗粒、硅酸钙颗粒、碳化硅颗粒、聚合物颗粒、金属颗粒、炭黑颗粒、石墨烯颗粒、石墨颗粒、金刚石颗粒和耐火材料。
18.根据权利要求15所述的方法，其中，在聚合物向陶瓷转化的所述过程中，所述预应变通过机器人或形状记忆合金或热膨胀或弛豫残余应力或激光切割晶格里的韧带或其组合来编程调节。
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CN114178704A (zh) * 2021-11-03 2022-03-15 香港城市大学深圳福田研究院 高温结构材料的制造方法以及前驱体

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