Direct 3D Printing of Ultralight Graphene Oxide Aerogel Microlattices

Graphene aerogel microlattices (GAMs) hold great prospects for many multifunctional applications due to their low density, high porosity, designed lattice structures, good elasticity, and tunable electrical conductivity. Previous 3D printing approaches to fabricate GAMs require either high content of additives or complex processes, limiting their wide applications. Here, a facile ion‐induced gelation method is demonstrated to directly print GAMs from graphene oxide (GO) based ink. With trace addition of Ca²⁺ ions as gelators, aqueous GO sol converts to printable gel ink. Self‐standing 3D structures with programmable microlattices are directly printed just in air at room temperature. The rich hierarchical pores and high electrical conductivity of GAMs bring admirable capacitive performance for supercapacitors. The gravimetric capacitance (C_s) of GAMs is 213 F g^?1 at 0.5 A g^?1 and 183 F g^?1 at 100 A g^?1, and retains over 90% after 50 000 cycles. The facile, direct 3D printing of neat graphene oxide can promote wide applications of GAMs from energy storage to tissue engineering scaffolds.     

Ultraprecise 3D Printed Graphene Aerogel Microlattices on Tape for Micro Sensors and E-Skin

3D printed graphene aerogels hold promise for flexible sensing fields due to their flexibility, low density, conductivity, and piezo-resistivity. However, low printing accuracy/fidelity and stochastic porous networks have hindered both sensing performance and device miniaturization. Here, printable graphene oxide (GO) inks are formulated through modulating oxygen functional groups, which allows printing of self-standing 3D graphene oxide aerogel microlattice (GOAL) with an ultra-high printing resolution of 70 µm. The reduced GOAL (RGOAL) is then stuck onto the adhesive tape as a facile and large-scale strategy to adapt their functionalities into target applications. Benefiting from the printing resolution of 70 µm, RGOAL tape shows better performance and data readability when used as micro sensors and robot e-skin. By adjusting the molecular structure of GO, the research realizes regulation of rheological properties of GO hydrogel and the 3D printing of lightweight and ultra-precision RGOAL, improves the sensing accuracy of graphene aerogel electronic devices and realizes the device miniaturization, expanding the application of graphene aerogel devices to a broader field such as micro robots, which is beyond the reach of previous reports.     

Photo-Curing 3D Printing of Thermosetting Sacrificial Tooling for Fabricating Fiber-Reinforced Hollow Composites

Carbon fiber-reinforced hollow composites play a vital role in lightweighting modern cars and aircrafts. Fabrication of such hollow composites with seamless internal finish requires sacrificial tooling that can be used under pressure and high temperature. For the very first time, high performance sacrificial tooling that can be used to fabricate fiber-reinforced hollow composites is produced using photocuring 3D printing technology. This is achieved by developing UV-curable resins containing highly soluble yet hydrolysable acetal acrylate cross-linker and hydrophilic 4-acryloylmorpholine monomer. It is found that the cross-linker content greatly affects the printing speed. Further, the widely adopted UV post-curing method is found to have negligible impact on improving the thermal-mechanical properties of printed structures. After thermal post-treatment, printed sacrificial tooling exhibits a heat deflection temperature of 112 °C at 0.455 MPa and an average coefficient of linear thermal expansion of 59 ppm °C⁻¹ between 30 and 100 °C. As a result, printed tooling enables fabrication of carbon fiber-reinforced hollow composites with complex geometry, which shows a tensile strength of 802 MPa and an elastic modulus of 50.2 GPa.     

Cellulose Nanocrystal Inks for 3D Printing of Textured Cellular Architectures

3D printing of renewable building blocks like cellulose nanocrystals offers an attractive pathway for fabricating sustainable structures. Here, viscoelastic inks composed of anisotropic cellulose nanocrystals (CNC) that enable patterning of 3D objects by direct ink writing are designed and formulated. These concentrated inks are composed of CNC particles suspended in either water or a photopolymerizable monomer solution. The shear‐induced alignment of these anisotropic building blocks during printing is quantified by atomic force microscopy, polarized light microscopy, and 2D wide‐angle X‐ray scattering measurements. Akin to the microreinforcing effect in plant cell walls, the alignment of CNC particles during direct writing yields textured composites with enhanced stiffness along the printing direction. The observations serve as an important step forward toward the development of sustainable materials for 3D printing of cellular architectures with tailored mechanical properties.     

3D Printing of Hydrogels for Stretchable Ionotronic Devices

In the booming development of flexible electronics represented by electronic skins, soft robots, and human–machine interfaces, 3D printing of hydrogels, an approach used by the biofabrication community, is drawing attention from researchers working on hydrogel-based stretchable ionotronic devices. Such devices can greatly benefit from the excellent patterning capability of 3D printing in three dimensions, as well as the free design complexity and easy upscale potential. Compared to the advanced stage of 3D bioprinting, 3D printing of hydrogel ionotronic devices is in its infancy due to the difficulty in balancing printability, ionic conductivity, shape fidelity, stretchability, and other functionalities. In this review, a guideline is provided on how to utilize the power of 3D printing in building high-performance hydrogel-based stretchable ionotronic devices mainly from a materials’ point of view, highlighting the systematic approach to balancing the printability, printing quality, and performance of printed devices. Various 3D printing methods for hydrogels are introduced, and then the ink design principles, balancing printing quality, printed functions, such as elastic conductivity, self-healing ability, and device (e.g., flexible sensors, shape-morphing actuators, soft robots, electroluminescent devices, and electrochemical biosensors) performances are discussed. In conclusion, perspectives on the future directions of this exciting field are presented.     

Mechanically Robust,Ultraelastic Hierarchical Foam with Tunable Properties via 3D Printing

A mechanically robust, ultraelastic foam with controlled multiscale architectures and tunable mechanical/conductive performance is fabricated via 3D printing. Hierarchical porosity, including both macro‐ and microscaled pores, are produced by the combination of direct ink writing (DIW), acid etching, and phase inversion. The thixotropic inks in DIW are formulated by a simple one‐pot process to disperse duo nanoparticles (nanoclay and silica nanoparticles) in a polyurethane suspension. The resulting lightweight foam exhibits tailorable mechanical strength, unprecedented elasticity (standing over 1000 compression cycles), and remarkable robustness (rapidly and fully recover after a load more than 20 000 times of its own weight). Surface coating of carbon nanotubes yields a conductive elastic foam that can be used as piezoresistivity sensor with high sensitivity. For the first time, this strategy achieves 3D printing of elastic foam with controlled multilevel 3D structures and mechanical/conductive properties. Moreover, the facile ink preparation method can be utilized to fabricate foams of various materials with desirable performance via 3D printing.     

Nanocellulose-Based Ink for Vertically 3D Printing Micro-Architectures with High-Resolution

Nanocellulose has become an important renewable component for composite inks, owing to its desirable physical properties, reinforcing capabilities, and tunable self-assembly behavior. However, it is difficult to improve the rheological performance of the nanocellulose-based composite to meet the requirement for 3D printing high resolution microarchitectures. Herein, a strategy is proposed that incorporation of amphiphilic molecular surfactant into nanocellulose gel can increase the molecular interaction via hydrophobic bonds and enhance the ink viscoelasticity. Following the design, a composite ink is formulated by adding xylan and Nonaethylene glycol monododecyl ether (C12E9) within nanocellulose gel. A new printing program is designed to achieve vertical writing of the composite ink and obtain free-standing micropillars and microhemispheres with high resolution in dozens of micrometers. The microhemisphere on an atomic force microscope (AFM) cantilever can be used as colloidal probe. This work proves that nanocellulose composite ink is a candidate for 3D printing functional devices with special microstructures.     

3D Printing of Strong and Tough Double Network Granular Hydrogels

Many soft natural tissues display a fascinating set of mechanical properties that remains unmatched by manmade counterparts. These unprecedented mechanical properties are achieved through an intricate interplay between the structure and locally varying the composition of these natural tissues. This level of control cannot be achieved in soft synthetic materials. To address this shortcoming, a novel 3D printing approach to fabricate strong and tough soft materials is introduced, namely double network granular hydrogels (DNGHs) made from compartmentalized reagents. This is achieved with an ink composed of microgels that are swollen in a monomer-containing solution; after the ink is additive manufactured, these monomers are converted into a percolating network, resulting in a DNGH. These DNGHs are sufficiently stiff to repetitively support tensile loads up to 1.3 MPa. Moreover, they are more than an order of magnitude tougher than each of the pure polymeric networks they are made from. It is demonstrated that this ink enables printing macroscopic, strong, and tough objects, which can optionally be rendered responsive, with high shape fidelity. The modular and robust fabrication of DNGHs opens up new possibilities to design adaptive, strong, and tough hydrogels that have the potential to advance, for example, soft robotic applications.     

Patterned Carbon Nitride–Based Hybrid Aerogel Membranes via 3D Printing for Broadband Solar Wastewater Remediation

Controlled scalable assembly of 2D building blocks into macroscopic 3D architectures is highly significant. However, the assembly of g‐C₃N₄ into tailored, 3D architectures is not yet reported. Here, a 3D printing methodology to enable the programmable construction of carbon nitride–based hybrid aerogel membranes with patterned macroscopic architectures is proposed. g‐C₃N₄ nanosheets (CNNS) are used as the building block, and sodium alginate (SA) increases the viscosity of the ink to obtain the desired rheological properties. Three printing routes, including printing directly in air and in the supporting reservoirs composed of CaCl₂/glycerol solution or Pluronic F127, are demonstrated for printing versatility. The printed Au nanobipyramid–CNNS–SA hybrid aerogels exhibit broadband visible‐light absorption and superior solar wastewater remediation performance with excellent cyclic stability and easy manipulation features. Remarkably, the activity of the 3D‐printed aerogel is about 2.5 times of that of the contrast sample, attributing to the enhanced liquid velocity and solution diffusion efficiency because of the 3D‐printed structure, which is demonstrated by experimental and theoretical simulations. This approach can be extended to the macroscopic assembly of other 2D materials for myriad applications.     

4D Printing at the Microscale

3D printing of adaptive and dynamic structures, also known as 4D printing, is one of the key challenges in contemporary materials science. The additional dimension refers to the ability of 3D printed structures to change their properties—for example, shape—over time in a controlled fashion as the result of external stimulation. Within the last years, significant efforts have been undertaken in the development of new responsive materials for printing at the macroscale. However, 4D printing at the microscale is still in its early stages. Thus, this progress report will focus on emerging materials for 4D printing at the microscale as well as their challenges and potential applications. Hydrogels and liquid crystalline and composite materials have been identified as the main classes of materials representing the state of the art of the growing field. For each type of material, the challenges and critical barriers in the material design and their performance in 4D microprinting are discussed. Importantly, further necessary strategies are proposed to overcome the limitations of the current approaches and move toward their application in fields such as biomedicine, microrobotics, or optics.     

Graphene Oxide Based Transparent Resins For Accurate 3D Printing of Conductive Materials

Digital Light Processing (DLP) allows the fast realization of 3D objects with high spatial resolution. However, DLP is limited to transparent resins, and therefore not well suited for printing electrically conductive materials. Manufacturing conductive materials will significantly broaden the spectrum of applications of the DLP technology. But conductive metals or carbon-based fillers absorb and scatter light; inhibiting thereby photopolymerization, and lowering resolution. In this study, UV transparent liquid crystal graphene oxide (GO) is used as precursor for generating in situ conductive particles. The GO materials are added to a photopolymerizable resin via an original solvent exchange process. By contrast to earlier contributions, the absence of drying during the all process allows the GO material to be transferred as monolayers to limit UV scattering. The absence of UV scattering and absorption allows for fast and high-resolution 3D printing. The chosen resin sustain high temperature to enable an in situ efficient thermal reduction of GO into reduced graphene oxide (rGO) that is electrically conductive. The rGO particles form percolated networks with conductivities up to 1.2 × 10⁻² S m⁻¹. The present method appears therefore as a way to reconcile the DLP technology with the manufacturing of 3D electrically conductive objects.     

Femtosecond Laser 4D Printing of Light-Driven Intelligent Micromachines

Intelligent micromachines that respond to external light stimuli have a broad range of potential applications, such as microbots, biomedicine, and adaptive optics. However, artificial light-driven intelligent micromachines with a low actuation threshold, rapid responsiveness, and designable and precise 3D transformation capability remain unachievable to date. Here, a single-material and one-step 4D printing strategy are proposed to enable the nanomanufacturing of agile and low-threshold light-driven 3D micromachines with programmable shape-morphing characteristics. The as-developed carbon nanotube-doped composite hydrogel simultaneously enhanced the light absorption, thermal conductivity, and mechanical modulus of the crosslinked network, thus significantly increasing the light sensitivity and response speed of micromachines. Moreover, the structural design and assembly of asymmetric microscale mechanical metamaterial unit cells enable the highly efficient additive nanomanufacturing of 3D shape-morphable micromachines with large dynamic modulation and spatiotemporal controllability. Using this strategy, the world's smallest artificial beating heart with programmable light-stimulus responsiveness for the cardiac cycle is successfully printed. This 4D printing method paves the way for the construction of multifunctional intelligent micromachines for bionics, drug delivery, integrated microsystems, and other fields.     

Mechanical Properties Tailoring of 3D Printed Photoresponsive Nanocellulose Composites

3D printing technologies allow control over the alignment of building blocks in synthetic materials, but compositional changes often require complex multimaterial printing steps. Here, 3D printable materials showing locally tunable mechanical properties are produced in a single printing step of Direct Ink Writing. These new inks consist of a polymer matrix bearing biocompatible photoreactive cinnamate derivatives and up to 30 wt% of anisotropic cellulose nanocrystals. The printed materials are mechanically versatile and can undergo further crosslinking upon illumination. When illuminating the material and controlling the irradiation doses, the Young's moduli can be adjusted between 15 and 75 MPa. Moreover, spatially controlled illumination allows patterning stiff geometries, resulting in 3D printed structures with segments of different mechanical properties tailoring the mechanical behavior under compression. The high design freedom implemented by 3D printing and photopatternability opens the venue to rapid manufacturing of devices for applications such as prosthetics or soft robotics where the 3D shapes and mechanical properties must be tailored for personalized load cases.     

Multi-Fidelity High-Throughput Optimization of Electrical Conductivity in P3HT-CNT Composites

Combining high-throughput experiments with machine learning accelerates materials and process optimization toward user-specified target properties. In this study, a rapid machine learning-driven automated flow mixing setup with a high-throughput drop-casting system is introduced for thin film preparation, followed by fast characterization of proxy optical and target electrical properties that completes one cycle of learning with 160 unique samples in a single day, a > 10 ×  improvement relative to quantified, manual-controlled baseline. Regio-regular poly-3-hexylthiophene is combined with various types of carbon nanotubes, to identify the optimum composition and synthesis conditions to realize electrical conductivities as high as state-of-the-art 1000 S cm⁻¹. The results are subsequently verified and explained using offline high-fidelity experiments. Graph-based model selection strategies with classical regression that optimize among multi-fidelity noisy input-output measurements are introduced. These strategies present a robust machine-learning driven high-throughput experimental scheme that can be effectively applied to understand, optimize, and design new materials and composites.     

三维打印的现状与未来

三维打印是一种增材制造工艺,其愿景是未来可以在任何地方（Anywhere）制作任何构造（Any-composition）、任何材料（Any-material）和任何几何形状（Any-geometry）的实物.综述了该技术的特点和优势,近年来在成本价格和材料方面的技术突破,以及新的应用领域.并探讨可能带来的商务范式、生产模式和生活方式的变革.最后指出该类技术的局限性和未来发展前景.     

Dynamic Photomask‐Assisted Direct Ink Writing Multimaterial for Multilevel Triboelectric Nanogenerator

Triboelectric nanogenerator (TENG) devices are extensively studied as a mechanical energy harvester and self‐powered sensor for wearable electronics and physiological monitoring. However, the conventional TENG fabrication involving assembling steps and using the single property of matrix material suffers from simple devices shape and a single level of mechanical response for sensing and energy harvesting. Here, the printed multimaterial matrix for multilevel mechanical‐responsive TENG with on‐demand reconfiguration of shape is reported. A multimaterial 3D printing approach by using dynamic photomask‐assisted direct ink writing printing together with a two‐stage curing hybrid ink is first developed. Multimaterial structures with location‐specific properties, such as tensile modulus, failure stress, and glass transition temperature for controlled deformation, crack propagation path, and sequential shape memory, are directly printed. The printed multimaterial structure with sequential deformation behavior is used to fabricate a multilevel‐TENG (mTENG) device for multiple level mechanical energy harvesters and sensors. It is demonstrated that the mTENG can be embedded in shoe insoles to achieve both comfortable wearing and motion state monitoring. This work provides a new approach to combine multimaterial 3D printing with TENG devices for functional wearable electronics as energy harvester and sensors.     

3D Printing of Multifunctional Hydrogels

3D printing technology has been widely explored for the rapid design and fabrication of hydrogels, as required by complicated soft structures and devices. Here, a new 3D printing method is presented based on the rheology modifier of Carbomer for direct ink writing of various functional hydrogels. Carbomer is shown to be highly efficient in providing ideal rheological behaviors for multifunctional hydrogel inks, including double network hydrogels, magnetic hydrogels, temperature‐sensitive hydrogels, and biogels, with a low dosage (at least 0.5% w/v) recorded. Besides the excellent printing performance, mechanical behaviors, and biocompatibility, the 3D printed multifunctional hydrogels enable various soft devices, including loadable webs, soft robots, 4D printed leaves, and hydrogel Petri dishes. Moreover, with its unprecedented capability, the Carbomer‐based 3D printing method opens new avenues for bioprinting manufacturing and integrated hydrogel devices.     

3D打印专利技术的国内主要申请人分析

对3D打印技术进行了简介,并且根据设定的关键词、IPC分类号等对涉及3D打印技术的中国已公开专利进行检索,列出了国内前14位申请人,通过对其中5位申请人的专利申请的情况(申请类型、申请状态等)的统计分析,总结其各自的专利申请的特点,并进行了各申请人之间的比较及建议,对我国相关企业的研发和专利申请提出了建议.     

3D Printable One-Part Carbon Nanotube-Elastomer Ink for Health Monitoring Applications

3D printing of conductive elastomers is a promising route to personalized health monitoring applications due to its flexibility and biocompatibility. Here, a one-part, highly conductive, flexible, stretchable, 3D printable carbon nanotube (CNT)-silicone composite is developed and thoroughly characterized. The one-part nature of the inks: i) enables printing without prior mixing and cures under ambient conditions; ii) allows direct dispensing at ≈100 µm resolution printability on nonpolar and polar substrates; iii) forms both self-supporting and high-aspect-ratio structures, key aspects in additive biomanufacturing that eliminate the need for sacrificial layers; and iv) lends efficient, reproducible, and highly sensitive responses to various tensile and compressive stimuli. The high electrical and thermal conductivity of the CNT-silicone composite is further extended to facilitate use as a flexible and stretchable heating element, with applications in body temperature regulation, water distillation, and dual temperature sensing and Joule heating. Overall, the facile fabrication of this composite points to excellent synergy with direct ink writing and can be used to prepare patient-specific wearable electronics for motion detection and cardiac and respiratory monitoring devices and toward advanced personal health tracking and bionic skin applications.     

A Subtractive Photoresist Platform for Micro‐ and Macroscopic 3D Printed Structures

The selective removal of structural elements plays a decisive role in 3D printing applications enabling complex geometries. To date, the fabrication of complex structures on the microscale is severely limited by multistep processes. Herein, a subtractive photoresist platform technology that is transferable from microscopic 3D printing via direct laser writing to macroscopic structures via stereolithography is reported. All resist components are readily accessible and exchangeable, offering fast adaptation of the resist's property profile. The micro‐ and macroprinted structures can be removed in a facile fashion, without affecting objects based on standard photoresists. The cleavage is analyzed by time‐lapse optical microscopy as well as via in‐depth spectroscopic assessment. The mechanical properties of the printed materials are investigated by nanoindentation. Critically, the power of the subtractive resist platform is demonstrated by constructing complex 3D objects with flying features on the microscale.