High‐Performance Materials for 3D Printing in Chemical Synthesis Applications

3D printing has emerged as an enabling technology for miniaturization. High‐precision printing techniques such as stereolithography are capable of printing microreactors and lab‐on‐a‐chip devices for efficient parallelization of biological and biochemical reactions under reduced uptake of reactants. In the world of chemistry, however, up until now, miniaturization has played a minor role. The chemical and thermal stability of regular 3D printing resins is insufficient for sustaining the harsh conditions of chemical reactions. Novel material formulations that produce highly stable 3D‐printed chips are highly sought for bringing chemistry up‐to‐date on the development of miniaturization. In this work, a brief review of recent developments in highly stable materials for 3D printing is given. This work focuses on three highly stable 3D‐printable material systems: transparent silicate glasses, ceramics, and fluorinated polymers. It is further demonstrated that 3D printing is also a versatile technique for surface structuring of polymers to enhance their wetting performance. Such micro/nanostructuring is key to selectively wetting surface patterns that are versatile for chemical arrays and droplet synthesis.     

Electrohydrodynamic 3D printing of orderly carbon/nickel composite network as supercapacitor electrodes

Electrohydrodynamic(EHD)3D printing of carbon-based materials in the form of orderly networks can have various applications.In this work,microscale carbon/nickel(C-Ni)composite electrodes with con-trolled porosity have been utilized in electrochemical energy storage of supercapacitors.Polyacrylonitrile(PAN)was chosen as the basic material for its excellent carbonization performance and EHD print-ing property.Nickel nitrate(Ni(NO3)2)was incorporated to form Ni nanoparticles which can improve the conductivity and the capacitance performance of the electrode.Well-aligned PAN-Ni(NO3)2 com-posite structures have been fabricated and carbonized as C-Ni electrodes with the typical diameter of 9.2±2.1 μm.The porosity of the as-prepared C-Ni electrode can be controlled during the EHD process.Electrochemical results show the C-Ni network electrode has achieved a 2.3 times higher areal specific capacitance and 1.7 times higher mass specific capacitance than those of a spin-coated electrode.As such,this process offers a facile and scalable strategy for the fabrication of orderly carbon-based conductive structures for various applications such as energy storage devices and printable electronics.     

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.     

3D Printing of Living Responsive Materials and Devices

3D printing has been intensively explored to fabricate customized structures of responsive materials including hydrogels, liquid‐crystal elastomers, shape‐memory polymers, and aqueous droplets. Herein, a new method and material system capable of 3D‐printing hydrogel inks with programed bacterial cells as responsive components into large‐scale (3 cm), high‐resolution (30 μm) living materials, where the cells can communicate and process signals in a programmable manner, are reported. The design of 3D‐printed living materials is guided by quantitative models that account for the responses of programed cells in printed microstructures of hydrogels. Novel living devices are further demonstrated, enabled by 3D printing of programed cells, including logic gates, spatiotemporally responsive patterning, and wearable devices.     

Machine Learning-Informed Predictive Design and Analysis of Electrohydrodynamic Printing Systems

Electrohydrodynamic (EHD) processes are promising techniques for manufacturing nanoscopic products with different shapes (such as thin films, nanofibers, 2D/3D nanostructures, and nanoparticles) and materials at a low cost using simple equipment. A key challenge in their adoption by nonexperts is the requirement of enormous time and resources in identifying the optimum design/process parameters for the underlying material and EHD system. Machine learning (ML) has made exciting advancements in predictive modeling of different processes, provided it is trained on high-quality datasets at appropriate volumes. This article extends the suitability of such ML-enabled approaches to a new technological domain of EHD spraying and drop-on-demand printing. Different ML models like ridge regression, random forest regression, support vector regression, gradient boosting regression, and multilayer perceptron are trained and their performance using evaluation metrics like RMSE and R2_score is examined. Tree-based algorithms like gradient boosting regression are found to be the most suitable technique for modeling EHD processes. The trained ML models show substantially higher accuracy (average error < 5%) in replicating these nonlinear processes as compared to previously reported scaling laws (average error ≈ 42%) and are well suited for predictive modeling/analysis of the underlying EHD system and process.     

3D‐Printed,All‐in‐One Evaporator for High‐Efficiency Solar Steam Generation under 1 Sun Illumination

Using solar energy to generate steam is a clean and sustainable approach to addressing the issue of water shortage. The current challenge for solar steam generation is to develop easy‐to‐manufacture and scalable methods which can convert solar irradiation into exploitable thermal energy with high efficiency. Although various material and structure designs have been reported, high efficiency in solar steam generation usually can be achieved only at concentrated solar illumination. For the first time, 3D printing to construct an all‐in‐one evaporator with a concave structure for high‐efficiency solar steam generation under 1 sun illumination is used. The solar‐steam‐generation device has a high porosity (97.3%) and efficient broadband solar absorption (>97%). The 3D‐printed porous evaporator with intrinsic low thermal conductivity enables heat localization and effectively alleviates thermal dissipation to the bulk water. As a result, the 3D‐printed evaporator has a high solar steam efficiency of 85.6% under 1 sun illumination (1 kW m^?2), which is among the best compared with other reported evaporators. The all‐in‐one structure design using the advanced 3D printing fabrication technique offers a new approach to solar energy harvesting for high‐efficiency steam generation.     

3D Printed Polymer Photodetectors

Extrusion‐based 3D printing, an emerging technology, has been previously used in the comprehensive fabrication of light‐emitting diodes using various functional inks, without cleanrooms or conventional microfabrication techniques. Here, polymer‐based photodetectors exhibiting high performance are fully 3D printed and thoroughly characterized. A semiconducting polymer ink is printed and optimized for the active layer of the photodetector, achieving an external quantum efficiency of 25.3%, which is comparable to that of microfabricated counterparts and yet created solely via a one‐pot custom built 3D‐printing tool housed under ambient conditions. The devices are integrated into image sensing arrays with high sensitivity and wide field of view, by 3D printing interconnected photodetectors directly on flexible substrates and hemispherical surfaces. This approach is further extended to create integrated multifunctional devices consisting of optically coupled photodetectors and light‐emitting diodes, demonstrating for the first time the multifunctional integration of multiple semiconducting device types which are fully 3D printed on a single platform. The 3D‐printed optoelectronic devices are made without conventional microfabrication facilities, allowing for flexibility in the design and manufacturing of next‐generation wearable and 3D‐structured optoelectronics, and validating the potential of 3D printing to achieve high‐performance integrated active electronic materials and devices.     

3D Nanoprinted Plastic Kinoform X‐Ray Optics

High‐performance focusing of X‐rays requires the realization of very challenging 3D geometries with nanoscale features, sub‐millimeter‐scale apertures, and high aspect ratios. A particularly difficult structure is the profile of an ideal zone plate called a kinoform, which is manufactured in nonideal approximated patterns, nonetheless requires complicated multistep fabrication processes. Here, 3D fabrication of high‐performance kinoforms with unprecedented aspect ratios out of low‐loss plastics using femtosecond two‐photon 3D nanoprinting is presented. A thorough characterization of the 3D‐printed kinoforms using direct soft X‐ray imaging and ptychography demonstrates superior performance with an efficiency reaching up to 20%. An extended concept is proposed for on‐chip integration of various X‐ray optics toward high‐fidelity control of X‐ray wavefronts and ultimate efficiencies even for harder X‐rays. Initial results establish new, advanced focusing optics for both synchrotron and laboratory sources for a large variety of X‐ray techniques and applications ranging from materials science to medicine.     

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。     

Biotinylated Photopolymers for 3D‐Printed Unibody Lab‐on‐a‐Chip Optical Platforms

The present work reports the first demonstration of straightforward fabrication of monolithic unibody lab‐on‐a‐chip (ULOCs) integrating bioactive micrometric 3D scaffolds by means of multimaterial stereolithography (SL). To this end, a novel biotin‐conjugated photopolymer is successfully synthesized and optimally formulated to achieve high‐performance SL‐printing resolution, as demonstrated by the SL‐fabrication of biotinylated structures smaller than 100 µm. By optimizing a multimaterial single‐run SL‐based 3D‐printing process, such biotinylated microstructures are incorporated within perfusion microchambers whose excellent optical transparency enables real‐time optical microscopy analyses. Standard biotin‐binding assays confirm the existence of biotin‐heads on the surfaces of the embedded 3D microstructures and allow to demonstrate that the biofunctionality of biotin is not altered during the SL‐printing, thus making it exploitable for further conjugation with other biomolecules. As a step forward, an in‐line optical detection system is designed, prototyped via SL‐printing and serially connected to the perfusion microchambers through customized world‐to‐chip connectors. Such detection system is successfully employed to optically analyze the solution flowing out of the microchambers, thus enabling indirect quantification of the concentration of target interacting biomolecules. The successful application of this novel biofunctional photopolymer as SL‐material enables to greatly extend the versatility of SL to directly fabricate ULOCs with intrinsic biofunctionality.     

3D Printing of Ultralight Biomimetic Hierarchical Graphene Materials with Exceptional Stiffness and Resilience

Biological materials with hierarchical architectures (e.g., a macroscopic hollow structure and a microscopic cellular structure) offer unique inspiration for designing and manufacturing advanced biomimetic materials with outstanding mechanical performance and low density. Most conventional biomimetic materials only benefit from bioinspired architecture at a single length scale (e.g., microscopic material structure), which largely limits the mechanical performance of the resulting materials. There exists great potential to maxime the mechanical performance of biomimetic materials by leveraging a bioinspired hierarchical structure. An ink‐based three‐dimensional (3D) printing strategy to manufacture an ultralight biomimetic hierarchical graphene material (BHGMs) with exceptionally high stiffness and resilience is demonstrated. By simultaneously engineering 3D‐printed macroscopic hollow structures and constructing an ice‐crystal‐induced cellular microstructure, BHGMs can achieve ultrahigh elasticity and stability at compressive strains up to 95%. Multiscale finite element analyses indicate that the hierarchical structures of BHGMs effectively reduce the macroscopic strain and transform the microscopic compressive deformation into the rotation and bending of the interconnected graphene flakes. This 3D printing strategy demonstrates the great potential that exists for the assembly of other functional materials into hierarchical cellular structures for various applications where high stiffness and resilience at low density are simultaneously required.     

3D Printed Functional and Biological Materials on Moving Freeform Surfaces

Conventional 3D printing technologies typically rely on open‐loop, calibrate‐then‐print operation procedures. An alternative approach is adaptive 3D printing, which is a closed‐loop method that combines real‐time feedback control and direct ink writing of functional materials in order to fabricate devices on moving freeform surfaces. Here, it is demonstrated that the changes of states in the 3D printing workspace in terms of the geometries and motions of target surfaces can be perceived by an integrated robotic system aided by computer vision. A hybrid fabrication procedure combining 3D printing of electrical connects with automatic pick‐and‐placing of surface‐mounted electronic components yields functional electronic devices on a free‐moving human hand. Using this same approach, cell‐laden hydrogels are also printed on live mice, creating a model for future studies of wound‐healing diseases. This adaptive 3D printing method may lead to new forms of smart manufacturing technologies for directly printed wearable devices on the body and for advanced medical treatments.     

Freestanding 3D Mesostructures,Functional Devices,and Shape‐Programmable Systems Based on Mechanically Induced Assembly with Shape Memory Polymers

Capabilities for controlled formation of sophisticated 3D micro/nanostructures in advanced materials have foundational implications across a broad range of fields. Recently developed methods use stress release in prestrained elastomeric substrates as a driving force for assembling 3D structures and functional microdevices from 2D precursors. A limitation of this approach is that releasing these structures from their substrate returns them to their original 2D layouts due to the elastic recovery of the constituent materials. Here, a concept in which shape memory polymers serve as a means to achieve freestanding 3D architectures from the same basic approach is introduced, with demonstrated ability to realize lateral dimensions, characteristic feature sizes, and thicknesses as small as ≈500, 10, and 5 µm simultaneously, and the potential to scale to much larger or smaller dimensions. Wireless electronic devices illustrate the capacity to integrate other materials and functional components into these 3D frameworks. Quantitative mechanics modeling and experimental measurements illustrate not only shape fixation but also capabilities that allow for structure recovery and shape programmability, as a form of 4D structural control. These ideas provide opportunities in fields ranging from micro‐electromechanical systems and microrobotics, to smart intravascular stents, tissue scaffolds, and many others.     

Progress in 3D Printing of Carbon Materials for Energy‐Related Applications

The additive‐manufacturing (AM) technique, known as three‐dimensional (3D) printing, has attracted much attention in industry and academia in recent years. 3D printing has been developed for a variety of applications. Printable inks are the most important component for 3D printing, and are related to the materials, the printing method, and the structures of the final 3D‐printed products. Carbon materials, due to their good chemical stability and versatile nanostructure, have been widely used in 3D printing for different applications. Good inks are mainly based on volatile solutions having carbon materials as fillers such as graphene oxide (GO), carbon nanotubes (CNT), carbon blacks, and solvent, as well as polymers and other additives. Studies of carbon materials in 3D printing, especially GO‐based materials, have been extensively reported for energy‐related applications. In these circumstances, understanding the very recent developments of 3D‐printed carbon materials and their extended applications to address energy‐related challenges and bring new concepts for material designs are becoming urgent and important. Here, recent developments in 3D printing of emerging devices for energy‐related applications are reviewed, including energy‐storage applications, electronic circuits, and thermal‐energy applications at high temperature. To close, a conclusion and outlook are provided, pointing out future designs and developments of 3D‐printing technology based on carbon materials for energy‐related applications and beyond.     

3D Nanoprinting of Perovskites

As competing with the established silicon technology, organic–inorganic metal halide perovskites are continually gaining ground in optoelectronics due to their excellent material properties and low‐cost production. The ability to have control over their shape, as well as composition and crystallinity, is indispensable for practical materialization. Many sophisticated nanofabrication methods have been devised to shape perovskites; however, they are still limited to in‐plane, low‐aspect‐ratio, and simple forms. This is in stark contrast with the demands of modern optoelectronics with freeform circuitry and high integration density. Here, a nanoprecision 3D printing is developed for organic–inorganic metal halide perovskites. The method is based on guiding evaporation‐induced perovskite crystallization in mid‐air using a femtoliter ink meniscus formed on a nanopipette, resulting in freestanding 3D perovskite nanostructures with a preferred crystal orientation. Stretching the ink meniscus with a pulling process enables on‐demand control of the nanostructure's diameter and hollowness, leading to an unprecedented tubular‐solid transition. With varying the pulling direction, a layer‐by‐layer stacking of perovskite nanostructures is successfully demonstrated with programmed shapes and positions, a primary step for additive manufacturing. It is expected that the method has the potential to create freeform perovskite nanostructures for customized optoelectronics.     

Development of Bioimplants with 2D, 3D,and 4D Additive Manufacturing Materials

Over the past 30 years, additive manufacturing (AM) has developed rapidly and has demonstrated great potential in biomedical applications. AM is a materials-oriented manufacturing technology, since the solidification mechanism, architecture resolution, post-treatment process, and functional application are based on the materials to be printed. However, 3D printable materials are still quite limited for the fabrication of bioimplants. In this work, 2D/3D AM materials for bioimplants are reviewed. Furthermore, inspired by Tai Chi, a simple yet novel soft/rigid hybrid 4D AM concept is advanced to develop complex and dynamic biological structures in the human body based on 4D printing hybrid ceramic precursor/ceramic materials that were previously developed by our group. With the development of multi-material printing technology, the development of bioimplants and soft/rigid hybrid biological structures with 2D/3D/4D AM materials can be anticipated.     

Lignin‐Based Direct Ink Printed Structural Scaffolds

3D printing of lignocellulosic biomass (cellulose, hemicellulose, and lignin) has attracted increasing attention by using this abundant, sustainable, and ecofriendly material. While cellulose can be easily tailored into a highly viscous ink for 3D printing, after solvent evaporation, the final printed structures become highly porous, fragile, and easily fall apart in water due to its hydrophilic nature. Lignin, another crucial component of natural lignocellulose, has not yet been reported for ink printing due to its unfavorable rheological behavior. Herein, a low‐cost direct ink printing strategy is developed to fabricate lignin‐based 3D structures with lignin no further refined and a more compact microstructure as well as different functionalities compared with printed cellulose. By using a soft triblock copolymer as the crosslinking agent, the rheology of lignin‐based inks can be adjusted from soft to rigid, and even enables vertical printing which requires stiff and self‐supporting features. The lignin‐based inks contain less water (≈40 wt%) and exhibit a much denser, stiffer structure, resulting in a wet tensile strength of ≈30 MPa, compared to only ≈0.6 MPa for printed cellulose. In addition, the unique macromolecular structure of lignin also demonstrates significantly improved stability in water and under heat, as well as UV‐blocking performance.     

3D‐Printed Biomimetic Super‐Hydrophobic Structure for Microdroplet Manipulation and Oil/Water Separation

Biomimetic functional surfaces are attracting increasing attention for various technological applications, especially the superhydrophobic surfaces inspired by plant leaves. However, the replication of the complex hierarchical microstructures is limited by the traditional fabrication techniques. In this paper, superhydrophobic micro‐scale artificial hairs with eggbeater heads inspired by Salvinia molesta leaf was fabricated by the Immersed surface accumulation three dimensional (3D) printing process. Multi‐walled carbon nanotubes were added to the photocurable resins to enhance the surface roughness and mechanical strength of the microstructures. The 3D printed eggbeater surface reveals interesting properties in terms of superhydrophobilicity and petal effect. The results show that a hydrophilic material can macroscopically behave as hydrophobic if a surface has proper microstructured features. The controllable adhesive force (from 23 μN to 55 μN) can be easily tuned with different number of eggbeater arms for potential applications such as micro hand for droplet manipulation. Furthermore, a new energy‐efficient oil/water separation solution based on our biomimetic structures was demonstrated. The results show that the 3D‐printed eggbeater structure could have numerous applications, including water droplet manipulation, 3D cell culture, micro reactor, oil spill clean‐up, and oil/water separation.     

3D,Reconfigurable, Multimodal Electronic Whiskers via Directed Air Assembly

A batch‐assembly technique for forming 3D electronics on shape memory polymer substrates is demonstrated and is used to create dense, highly sensitive, multimodal arrays of electronic whiskers. Directed air flow at temperatures above the substrate's glass transition temperature transforms planar photolithographically defined resistive sensors from 2D precursors into shape‐tunable, deterministic 3D assemblies. Reversible 3D assembly and flattening is achieved by exploiting the shape memory properties of the substrate, enabling context‐driven shape reconfiguration to isolate/enhance specific sensing modes. In particular, measurement schemes and device configurations are introduced that allow for the sensing of temperature, stiffness, contact force, proximity, and surface texture and roughness. The assemblies offer highly spatiotemporally resolved, wide‐range measurements of surface topology (50 nm to 500 µm), material stiffness (200 kPa to 7.5 GPa), and temperature (0–100 °C), with response times of <250 µs. The development of a scalable process for 3D assembly of reconfigurable electronic sensors, as well as the large breadth and sensitivity of complex sensing modes demonstrated, has applications in the growing fields of 3D assembly, electronic skin, and human–machine interfaces.     

Current status of 4D printing technology and the potential of light-reactive smart materials as 4D printable materials

The onset of multi-material 3D printing and the combination of smart materials into the printable material has led to the development of an exciting new technology called 4D printing. This paper will introduce the background and development into 4D printing, discuss water reactive 4D printing methods and temperature reactive 4D printing, modelling and simulation software, and future applications of this new technology. Smart materials that react to different external stimuli are described, along with the benefits of these smart materials and their potential use in 4D printing applications; specifically, existing light-reactive smart materials. 4D printing has the prospective to simplify the design and manufacturing of different products and the potential of automating actuation devices that naturally react to their environment without the need for human interaction, batteries, processors, sensors, and motors.