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.     

3D Printing of Interdigitated Dielectric Elastomer Actuators

Dielectric elastomer actuators (DEAs) are soft electromechanical devices that exhibit large energy densities and fast actuation rates. They are typically produced by planar methods and, thus, expand in‐plane when actuated. Here, reported is a method for fabricating 3D interdigitated DEAs that exhibit in‐plane contractile actuation modes. First, a conductive elastomer ink is created with the desired rheology needed for printing high‐fidelity, interdigitated electrodes. Upon curing, the electrodes are then encapsulated in a self‐healing dielectric matrix composed of a plasticized, chemically crosslinked polyurethane acrylate. 3D DEA devices are fabricated with tunable mechanical properties that exhibit breakdown fields of 25 V µm^?1 and actuation strains of up to 9%. As exemplars, printed are prestrain‐free rotational actuators and multi‐voxel DEAs with orthogonal actuation directions in large‐area, out‐of‐plane motifs.     

Particle‐Free Emulsions for 3D Printing Elastomers

3D printing is a rapidly growing field that requires the development of yield‐stress fluids that can be used in postprinting transformation processes. There is a limited number of yield‐stress fluids currently available with the desired rheological properties for building structures with small filaments (≤l00 µm) with high shape‐retention. A printing‐centric approach for 3D printing particle‐free silicone oil‐in‐water emulsions with a polymer additive, poly(ethylene oxide) is presented. This particular material structure and formulation is used to build 3D structure and to pattern at filament diameters below that of any other known material in this class. Increasing the molecular weight of poly(ethylene oxide) drastically increases the extensibility of the material without significantly affecting shear flow properties (shear yield stress and linear viscoelastic moduli). Higher extensibility of the emulsion correlates to the ability of filaments to span relatively large gaps (greater than 6 mm) when extruded at large tip diameters (330 µm) and the ability to extrude filaments at high print rates (20 mm s^?1). 3D printed structures with these extensible particle‐free emulsions undergo postprinting transformation, which converts them into elastomers. These elastomers can buckle and recover from extreme compressive strain with no permanent deformation, a characteristic not native to the emulsion.     

3D Particle-Free Printing of Biocompatible Conductive Hydrogel Platforms for Neuron Growth and Electrophysiological Recording

Electrically conductive 3D periodic microscaffolds are fabricated using a particle-free direct ink writing approach for use as neuronal growth and electrophysiological recording platforms. A poly (2-hydroxyethyl methacrylate)/pyrrole ink, followed by chemical in situ polymerization of pyrrole, enables hydrogel printing through nozzles as small as 1 µ m. These conductive hydrogels can pattern complex 2D and 3D structures and have good biocompatibility with test cell cultures ( ≈ 94.5% viability after 7 days). Hydrogel arrays promote extensive neurite outgrowth of cultured Aplysia californica pedal ganglion neurons. This platform allows extracellular electrophysiological recording of steady-state and stimulated electrical neuronal activities. In summation, this 3D conductive ink printing process enables the preparation of biocompatible and micron-sized structures to create customized in vitro electrophysiological recording platforms.     

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.     

Printing Reconfigurable Bundles of Dielectric Elastomer Fibers

Active soft materials that change shape on demand are of interest for a myriad of applications, including soft robotics, biomedical devices, and adaptive systems. Despite recent advances, the ability to rapidly design and fabricate active matter in complex, reconfigurable layouts remains challenging. Here, the 3D printing of core-sheath-shell dielectric elastomer fibers (DEF) and fiber bundles with programmable actuation is reported. Complex shape morphing responses are achieved by printing individually addressable fibers within 3D architectures, including vertical coils and fiber bundles. These DEF devices exhibit resonance frequencies up to 700 Hz and lifetimes exceeding 2.6 million cycles. The multimaterial, multicore-shell 3D printing method opens new avenues for creating active soft matter with fast programable actuation.     

Engineering Natural Pollen Grains as Multifunctional 3D Printing Materials

The development of multifunctional 3D printing materials from sustainable natural resources is a high priority in additive manufacturing. Using an eco-friendly method to transform hard pollen grains into stimulus-responsive microgel particles, we engineered a pollen-derived microgel suspension that can serve as a functional reinforcement for composite hydrogel inks and as a supporting matrix for versatile freeform 3D printing systems. The pollen microgel particles enabled the printing of composite inks and improved the mechanical and physiological stabilities of alginate and hyaluronic acid hydrogel scaffolds for 3D cell culture applications. Moreover, the particles endowed the inks with stimulus-responsive controlled release properties. The suitability of the pollen microgel suspension as a supporting matrix for freeform 3D printing of alginate and silicone rubber inks was demonstrated and optimized by tuning the rheological properties of the microgel. Compared with other classes of natural materials, pollen grains have several compelling features, including natural abundance, renewability, affordability, processing ease, monodispersity, and tunable rheological features, which make them attractive candidates to engineer advanced materials for 3D printing applications.     

3D Printing of Bilineage Constructive Biomaterials for Bone and Cartilage Regeneration

Owing to the different biological properties of articular cartilage and subchondral bone, it remains significant challenge to construct a bi‐lineage constructive scaffold. In this study, manganese (Mn)‐doped β‐TCP (Mn‐TCP) scaffolds with varied Mn contents are prepared by a 3D‐printing technology. The effects of Mn on the physicochemical properties, bioactivity, and corresponding mechanism for stimulating osteochondral regeneration are systematically investigated. The incorporation of Mn into β‐TCP lowers the lattices parameters and crystallization temperatures, but improves the scaffold density and compressive strength. The ionic products from Mn‐TCP significantly improve the proliferation of both rabbit chondrocytes and mesenchymal stem cells (rBMSCs), as well as promote the differentiation of chondrocytes and rBMSCs. The in vivo study shows that Mn‐TCP scaffolds distinctly improve the regeneration of subchondral bone and cartilage tissues as compared to TCP scaffolds, upon transplantation in rabbit osteochondral defects for 8 and 12 weeks. The mechanism is closely related to the Mn²⁺ ions significantly stimulated the proliferation and differentiation of chondrocytes through activating HIF pathway and protected chondrocytes from the inflammatory osteoarthritis environment by activating autophagy. These findings suggest that 3D‐printing of Mn‐containing scaffolds with improved physicochemical properties and bilineage bioactivities represents an intelligent strategy for regenerating osteochondral defects.     

3D-Printed Photoresponsive Liquid Crystal Elastomer Composites for Free-Form Actuation

Direct ink writing of liquid crystal elastomers (LCEs) offers a new opportunity to program geometries for a wide variety of shape transformation modes toward applications such as soft robotics. So far, most 3D-printed LCEs are thermally actuated. Herein, a 3D-printable photoresponsive gold nanorod (AuNR)/LCE composite ink is developed, allowing for photothermal actuation of the 3D-printed structures with AuNR as low as 0.1 wt.%. It is shown that the printed filament has a superior photothermal response with 27% actuation strain upon irradiation to near-infrared (NIR) light (808 nm) at 1.4 W cm⁻² (corresponding to 160 °C) under optimal printing conditions. The 3D-printed composite structures can be globally or locally actuated into different shapes by controlling the area exposed to the NIR laser. Taking advantage of the customized structures enabled by 3D printing and the ability to control locally exposed light, a light-responsive soft robot is demonstrated that can climb on a ratchet surface with a maximum speed of 0.284 mm s⁻¹ (on a flat surface) and 0.216 mm s⁻¹ (on a 30° titled surface), respectively, corresponding to 0.428 and 0.324 body length per min, respectively, with a large body mass (0.23 g) and thickness (1 mm).     

3D Printed Template-Assisted Casting of Biocompatible Polyvinyl Alcohol-Based Soft Microswimmers with Tunable Stability

The past decade has seen an upsurge in the development of small-scale magnetic robots for various biomedical applications. However, many of the reported designs comprise components with biocompatibility concerns. Strategies for fabricating biocompatible and degradable microrobots are required. In this study, polyvinyl alcohol (PVA)-based magnetic hydrogel microrobots with different morphologies and tunable stability are developed by combining a 3D printed template-assisted casting with a salting-out process. 3D sacrificial micromolds are prepared via direct laser writing to shape PVA-magnetic nanoparticle composite hydrogel microrobots with high architectural complexity. By adjusting the PVA composition and salting-out parameters, the hydrogel dissolubility can be customized. Due to their high mobility, tunable stability, and high biocompatibility, these PVA-based magnetic microrobots are suitable platforms for targeted drug and cell delivery.     

Polysiloxane Inks for Multimaterial 3d Printing of High-Permittivity Dielectric Elastomers

Dielectric elastomer transducers (DET) are promising candidates for electrically-driven soft robotics. However, the high viscosity and low yield stress of DET formulations prohibit 3D printing, the most common manufacturing method for designer soft actuators. DET inks optimized for direct ink writing (DIW) produce elastomers with high stiffness and mechanical losses, diminishing the utility of DET actuators. To address the antagonistic nature of processing and performance constraints, principles of capillary suspensions are used to engineer DIW DET inks. By blending two immiscible polysiloxane liquids with a filler, a capillary ink suspension is obtained, in which the ink rheology can be tuned independently of the elastomer electromechanical properties. Rheometry is performed to measure and optimize processibility as a function of filler and secondary liquid fraction. Including polar polysiloxanes as the secondary liquid produces a printed elastomer exhibiting a four-fold permittivity increase over commercial polydimethylsiloxane. The characterization and multimaterial printing into layered DET devices demonstrates that the immiscible capillary suspension improves the processability of the inks and enhances the properties of the elastomers, enabling actuation of the devices at comparatively low voltages. It is anticipated that this formulation approach will allow soft robotics to harness the full potential of DETs.     

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.     

Hybrid 3D Printing of Synthetic and Cell‐Laden Bioinks for Shape Retaining Soft Tissue Grafts

Despite recent advances in clinical procedures, the repair of soft tissue remains a reconstructive challenge. Current technologies such as synthetic implants and dermal flap autografting result in inefficient shape retention and unpredictable aesthetic outcomes. 3D printing, however, can be leveraged to produce superior soft tissue grafts that allow enhanced host integration and volume retention. Here, a novel dual bioink 3D printing strategy is presented that utilizes synthetic and natural materials to create stable, biomimetic soft tissue constructs. A double network ink composed of covalently cross‐linked poly(ethylene) glycol and ionically cross‐linked alginate acts as a physical support network that promotes cell growth and enables long‐term graft shape retention. This is coupled with a cell‐laden, biodegradable gelatin methacrylate bioink in a hybrid printing technique, and the composite scaffolds are evaluated in their mechanical properties, shape retention, and cytotoxicity. Additionally, a new shape analysis technique utilizing CloudCompare software is developed that expands the available toolbox for assessing scaffold aesthetic properties. With this dynamic 3D bioprinting strategy, complex geometries with robust internal structures can be easily modulated by varying the print ratio of nondegradable to sacrificial strands. The versatility of this hybrid printing fabrication platform can inspire the design of future multimaterial regenerative implants.     

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.     

机械三维建模及3D打印课程教学模式研究

三维建模软件在机械行业中越来越受到重视,相关软件的教学也成为机械大类专业的核心课程。以CREO 3.0为例,探讨了机械类三维建模课程的教学内容等到,并且进一步说明了作者在教学实践中的模式,在课程体系、教学资源建设、教学手段等方面都提出了新的理念和做法。     

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.     

In Situ Electrical Network Activation and Deactivation in Short Carbon Fiber Composites via 3D Printing

Prior studies on carbon-filler based, conductive polymer composites have mainly investigated how conductive filler morphology and concentration can tailor a material's electrical conductivity and overlooks the effects of filler alignment due to the difficulty to control and quickly quantify the filler alignment. Here, direct ink write 3D printing's unique ability is utilized to control carbon fiber alignment with a single process parameter, velocity ratio, to instantaneously activate or deactivate the electrical network in composites. Maximum electrical conductivity is achieved by randomly aligning carbon fibers that enhances the chance of direct fiber-to-fiber contact and, thus, activating the electrical network. However, aligning the fibers by increasing the velocity ratio disrupts the electrical network by minimizing fiber-to-fiber contact that resulted in a drastic decrease in electrical conductivity by as much as five orders of magnitude in both short and long carbon fiber composites. With this study, this study demonstrates that electrically conductive or insulative composites can be fabricated sequentially with a single ink. This novel ability to instantaneously control the electrical conductivity of carbon fiber reinforced composites allow to directly embed conductive pathways into designs to 3D print multifunctional composites that are capable of localized heating and self-sensing.     

3D Printing of Arbitrary Perovskite Nanowire Heterostructures

Deterministic integration of arbitrary semiconductor heterostructures opens a new class of modern electronics and optoelectronics. However, the realization of such heterostructures continues to suffer from impracticality, requiring energy- and labor-intensive, time-consuming fabrication processes. Here a 3D printing approach to fabricate freestanding metal halide perovskite nanowire heterostructures with a high degree of control over shape and composition is demonstrated. These features arise from freeform guiding of evaporation-driven perovskite crystallization by a femtoliter precursor meniscus formed on a printing nozzle. By using a double-barreled nanopipette as a printing nozzle, “all-at-once” heterostructure fabrication is achieved within seconds. The 3D-printed perovskite nanowire heterojunctions with multiple emission colors provide exciting optical functionalities such as programmable color mixing and encryption at the single nanopixel level. This “lithography-free” additive approach opens up the possibility to freely design and realize heterostructure-based devices without the constraints of traditional manufacturing processes.     

A Review of 3D Printing Technologies for Soft Polymer Materials

Soft polymer materials, which are similar to human tissues, have played critical roles in modern interdisciplinary research. Compared with conventional methods, 3D printing allows rapid prototyping and mass customization and is ideal for processing soft polymer materials. However, 3D printing of soft polymer materials is still in the early stages of development and is facing many challenges including limited printable materials, low printing resolution and speed, and poor functionalities. The present review aims to summarize the ideas to address these challenges. It focuses on three points: 1) how to develop printable materials and make unprintable materials printable, 2) how to choose suitable methods and improve printing resolution, and 3) how to directly construct functional structures/systems with 3D printing. After a brief introduction on this topic, the mainstream 3D printing technologies for printing soft polymer materials are reviewed, with an emphasis on improving printing resolution and speed, choosing suitable printing techniques, developing printable materials, and printing multiple materials. Moreover, the state‐of‐the‐art advancements in multimaterial 3D printing of soft polymer materials are summarized. Furthermore, the revolutions brought about by 3D printing of soft polymer materials for applications similar to biology are highlighted. Finally, viewpoints and future perspectives for this emerging field are discussed.