3‐D Printing and Development of Fluoropolymer Based Reactive Inks

Engineering reactive materials is an ever present goal in the energetics community. The desire is to have energetics configured in such a manner that performance is tailored and energy delivery can be targeted. Additive manufacturing (3‐D printing) is one area that could significantly improve our capabilities in this area, if adequate formulations are developed. In this paper, fluoropolymer based reactive inks are developed with micron (mAl) and nanoscale aluminum (nAl) serving, as the fuel at high solids loading (up to 67 wt%) and their viscosity required for 3‐D printing is detailed. For the pen‐type technique and valves used in this work, it is required to have viscosities on the order of 10⁴–10⁵ cP. For printed traces with apparent diameters under <500 μm, the combustion velocities for both micron and nano scale aluminum formulations, are approximately identical: 30 ± 3 versus 32 ± 2 mm s^?1, respectively. Further increasing the apparent diameter is shown to increase the combustion velocity in the case of the nanoscale aluminum formulation by four‐fold over that of the micron scale aluminum formulation, but it plateaus as it approaches an apparent diameter of 2 mm. The results suggest with proper architecture that tailorable combustion rates and energy delivery are feasible.

     

Stimuli-Triggered Multishape,Multimode, and Multistep Deformations Designed by Microfluidic 3D Droplet Printing

Elastomers generally possess low Young's modulus and high failure strain, which are widely used in soft robots and intelligent actuators. However, elastomers generally lack diverse functionalities, such as stimulated shape morphing, and a general strategy to implement these functionalities into elastomers is still challenging. Here, a microfluidic 3D droplet printing platform is developed to design composite elastomers architected with arrays of functional droplets. Functional droplets with controlled size, composition, position, and pattern are designed and implemented in the composite elastomers, imparting functional performances to the systems. The composited elastomers are sensitive to stimuli, such as solvent, temperature, and light, and are able to demonstrate multishape (bow- and S-shaped), multimode (gradual and sudden), and multistep (one- and two-step) deformations. Based on the unique properties of droplet-embedded composite elastomers, a variety of stimuli-responsive systems are developed, including designable numbers, biomimetic flowers, and soft robots, and a series of functional performances are achieved, presenting a facile platform to impart diverse functionalities into composite elastomers by microfluidic 3D droplet printing.     

3D Printing by Multiphase Silicone/Water Capillary Inks

3D printing of polymers is accomplished easily with thermoplastics as the extruded hot melt solidifies rapidly during the printing process. Printing with liquid polymer precursors is more challenging due to their longer curing times. One curable liquid polymer of specific interest is polydimethylsiloxane (PDMS). This study demonstrates a new efficient technique for 3D printing with PDMS by using a capillary suspension ink containing PDMS in the form of both precured microbeads and uncured liquid precursor, dispersed in water as continuous medium. The PDMS microbeads are held together in thixotropic granular paste by capillary attraction induced by the liquid precursor. These capillary suspensions possess high storage moduli and yield stresses that are needed for direct ink writing. They could be 3D printed and cured both in air and under water. The resulting PDMS structures are remarkably elastic, flexible, and extensible. As the ink is made of porous, biocompatible silicone that can be printed directly inside aqueous medium, it can be used in 3D printed biomedical products, or in applications such as direct printing of bioscaffolds on live tissue. This study demonstrates a number of examples using the high softness, elasticity, and resilience of these 3D printed structures.     

A New 3D Printing Strategy by Harnessing Deformation,Instability, and Fracture of Viscoelastic Inks

Direct ink writing (DIW) has demonstrated great potential as a multimaterial multifunctional fabrication method in areas as diverse as electronics, structural materials, tissue engineering, and soft robotics. During DIW, viscoelastic inks are extruded out of a 3D printer's nozzle as printed fibers, which are deposited into patterns when the nozzle moves. Hence, the resolution of printed fibers is commonly limited by the nozzle's diameter, and the printed pattern is limited by the motion paths. These limits have severely hampered innovations and applications of DIW 3D printing. Here, a new strategy to exceed the limits of DIW 3D printing by harnessing deformation, instability, and fracture of viscoelastic inks is reported. It is shown that a single nozzle can print fibers with resolution much finer than the nozzle diameter by stretching the extruded ink, and print various thickened or curved patterns with straight nozzle motions by accumulating the ink. A quantitative phase diagram is constructed to rationally select parameters for the new strategy. Further, applications including structures with tunable stiffening, 3D structures with gradient and programmable swelling properties, all printed with a single nozzle are demonstrated. The current work demonstrates that the mechanics of inks plays a critical role in developing 3D printing technology.     

高分子3D打印材料和打印工艺

3D打印技术亦称为增材制造,是基于三维数学模型数据,通过连续的物理层叠加,逐层增加材料来生成三维实体的技术。3D打印技术与传统材料加工技术相比有许多突出的优势,吸引了国内外工业界、投资界、学术界、新闻媒体和社会公众的热切关注。目前制约3D打印技术发展的因素主要有两个:打印工艺和打印材料。高分子聚合物在3D打印材料中占据主要地位。介绍了当前3D打印常用的高分子材料(热塑性高分子和光敏树脂)和与之相适应的打印工艺(FDM、SLS、SLA、Polyjet等),并对它们的特性和优缺点进行了评述,讨论了这些3D打印材料和工艺的开发面临的问题和挑战。     

基于UV油墨的3D地形图呈现

根据地形图的特点及UV油墨快速干燥的特性,提出一种运用3D建模和分层设色的方法,并通过实验,完成了中国台湾省主岛部分3D地形图的打印.选择台湾省主岛部分等高线图,在图形处理软件中,根据其高程,提取多幅等高线矢量图;根据墨层厚度与打印层数的定量关系,得到实际海拔高度与打印层数的对应关系,再根据等高线分层设色原理,设计分层设色对应表,并设定适当的比例尺,确定打印方案;使用喷墨打印机,打印得到具有一定立体感的3D彩色地形图.实验结果表明：根据UV油墨快速干燥的特点,使用UV喷墨打印机,可以打印得到具有立体效果的3D彩色地形图.     

Solution Mask Liquid Lithography (SMaLL) for One‐Step,Multimaterial 3D Printing

A novel methodology for printing 3D objects with spatially resolved mechanical and chemical properties is reported. Photochromic molecules are used to control polymerization through coherent bleaching fronts, providing large depths of cure and rapid build rates without the need for moving parts. The coupling of these photoswitches with resin mixtures containing orthogonal photo‐crosslinking systems allows simultaneous and selective curing of multiple networks, providing access to 3D objects with chemically and mechanically distinct domains. The power of this approach is showcased through the one‐step fabrication of bioinspired soft joints and mechanically reinforced “brick‐and‐mortar” structures.     

Rapid Open‐Air Digital Light 3D Printing of Thermoplastic Polymer

3D printing has witnessed a new era in which highly complexed customized products become reality. Realizing its ultimate potential requires simultaneous attainment of both printing speed and product versatility. Among various printing techniques, digital light processing (DLP) stands out in its high speed but is limited to intractable light curable thermosets. Thermoplastic polymers, despite their reprocessibility that allows more options for further manipulation, are restricted to intrinsically slow printing methods such as fused deposition modeling. Extending DLP to thermoplastics is highly desirable, but is challenging due to the need to reach rapid liquid–solid separation during the printing process. Here, a successful attempt at DLP printing of thermoplastic polymers is reported, realized by controlling two competing kinetic processes (polymerization and polymer dissolution) simultaneously occurring during printing. With a selected monomer, 4‐acryloylmorpholine (ACMO), printing of thermoplastic 3D scaffolds is demonstrated, which can be further converted into various materials/devices utilizing its unique water‐soluble characteristic. The ultralow viscosity of ACMO, along with surface oxygen inhibition, allows rapid liquid flow toward high‐speed open‐air printing. The process simplicity, enabling mechanism, and material versatility broaden the scope of 3D printing in constructing functional 3D devices including reconfigurable antenna, shape‐shifting structures, and microfluidics.     

A Review of 3D Printing Technology for Medical Applications

Donor shortages for organ transplantations are a major clinical challenge worldwide. Potential risks that are inevitably encountered with traditional methods include complications, secondary injuries, and limited source donors. Three-dimensional (3D) printing technology holds the potential to solve these limitations; it can be used to rapidly manufacture personalized tissue engineering scaffolds, repair tissue defects in situ with cells, and even directly print tissue and organs. Such printed implants and organs not only perfectly match the patient’s damaged tissue, but can also have engineered material microstructures and cell arrangements to promote cell growth and differentiation. Thus, such implants allow the desired tissue repair to be achieved, and could eventually solve the donor-shortage problem. This review summarizes relevant studies and recent progress on four levels, introduces different types of biomedical materials, and discusses existing problems and development issues with 3D printing that are related to materials and to the construction of extracellular matrix in vitro for medical applications.     

3D打印技术研究现状和关键技术EI北大核心CSCD

本文首先简要介绍了3D打印技术的基本原理及分类,然后重点介绍了有关金属材料3D打印的几种方法:电子束熔化成形(EBM)、激光选区熔化成形(SLM)、激光快速成形技术(LDMD)。简述了金属材料3D打印的应用领域及国内外发展情况及研究现状。文章最后结合国内外金属材料3D打印的研究现状,指出金属材料3D打印需要在打印用粉末、金属3D打印设备、3D打印零件无损检测方法、3D打印零件的失效行为和寿命预测等方面进行重点研究,并建立3D打印零件的无损检测标准规范以及3D打印材料全面力学性能数据库。     

超细水性油墨的研制

以苯乙烯和丙烯酸为聚合单体,甲苯为溶剂,采用溶液聚合法合成了水溶性颜料分散剂。以水溶性分散剂、颜料及助剂制备了超细颜料色浆,以自制乳液为连接料,加入超细颜料色浆,经分散、研磨制成了超细水性油墨,对超细油墨的细度、耐水性、光泽度等性能指标进行了测试。结果表明:超细水性油墨的细度为0.5～0.8μm,耐水性为5级,光泽度为0.8,优于目前水性油墨企业标准,其它性能指标符合水性油墨企业标准。     

3D Printing of Salt as a Template for Magnesium with Structured Porosity

Porosity is an essential feature in a wide range of applications that combine light weight with high surface area and tunable density. Porous materials can be easily prepared with a vast variety of chemistries using the salt‐leaching technique. However, this templating approach has so far been limited to the fabrication of structures with random porosity and relatively simple macroscopic shapes. Here, a technique is reported that combines the ease of salt leaching with the complex shaping possibilities given by additive manufacturing (AM). By tuning the composition of surfactant and solvent, the salt‐based paste is rheologically engineered and printed via direct ink writing into grid‐like structures displaying structured pores that span from the sub‐millimeter to the macroscopic scale. As a proof of concept, dried and sintered NaCl templates are infiltrated with magnesium (Mg), which is typically highly challenging to process by conventional AM techniques due to its highly oxidative nature and high vapor pressure. Mg scaffolds with well‐controlled, ordered porosity are obtained after salt removal. The tunable mechanical properties and the potential to be predictably bioresorbed by the human body make these Mg scaffolds attractive for biomedical implants and demonstrate the great potential of this additive technique.     

3D Printed Microfluidic Mixers—A Comparative Study on Mixing Unit Performances

One of the basic operations in microfluidic systems for biological and chemical applications is the rapid mixing of different fluids. However, flow profiles in microfluidic systems are laminar, which means molecular diffusion is the only mixing effect. Therefore, mixing structures are crucial to enable more efficient mixing in shorter times. Since traditional microfabrication methods remain laborious and expensive, 3D printing has emerged as a potential alternative for the fabrication of microfluidic devices. In this work, five different passive micromixers known from literature are redesigned in comparable dimensions and manufactured using high‐definition MultiJet 3D printing. Their mixing performance is evaluated experimentally, using sodium hydroxide and phenolphthalein solutions, and numerically via computational fluid dynamics. Both experimental and numerical analysis results show that HC and Tesla‐like mixers achieve complete mixing after 0.99 s and 0.78 s, respectively, at the highest flow rate (Reynolds number (Re) = 37.04). In comparison, Caterpillar mixers exhibit a lower mixing rate with complete mixing after 1.46 s and 1.9 s. Furthermore, the HC mixer achieves very good mixing performances over all flow rates (Re = 3.7 to 37.04), while other mixers show improved mixing only at higher flow rates.