3D Printing of Resilin in Water by Multiphoton Absorption Polymerization

Resilin is an elastic rubber-like protein found in the cuticles of insects. It incorporates outstanding properties of high resilience and fatigue lifetime, where kinetic energy storage is needed for biological functions such as flight and jumps. Since resilin is rich in tyrosine groups, localized photopolymerization is enabled due to the ability to introduce di-tyrosine bonds by a ruthenium-based photoinitiator. Using Multiphoton Absorption Polymerization 3D printing process, objects containing 100% recombinant resilin protein are printed in water at a submicron length scale. Consequently, protein-based hydrogels with complex structures are printed using space positioning voxel polymerization. The objects are characterized by dynamic mechanical analysis using nanoindentation. Printing parameters such as printing speed and laser power are found to enable tuning the mechanical properties of the printed objects. The printed objects are soft and resilient, similar to native resilin, while presenting the highest resolution of a structure made entirely of a protein and better mechanical properties of common hydrogels and poly(dimethylsiloxane). Moreover, topography and mechanical properties enable cell growth and alignment without cell adhesion primers, thus facilitating biological applications. The fabrication of 3D resilin-based hydrogel will open the way for potential applications based on biomimicking and in creating new functional objects.     

2D Janus Hybrid Materials of Polymer‐Grafted Carbon Nanotube/Graphene Oxide Thin Film as Flexible,Miniature Electric Carpet

Ultrathin, freestanding polymer hybrid film with macroscopic sizes and molecular thicknesses have received significant interest due to their applications as functional devices, microsensors or nanoactuators. Herein, a 2D Janus hybrid of polymer‐grafted carbon nanotubes/graphene oxide (CNTs/GO) thin film is fabricated using microcontact printed CNTs/GO as photo active surface to grow polymer brushes by self‐initiated photografting and photopolymerization selectively from one side of CNTs/GO film. This achieved 2D Janus hybrid materials with grafted polymer layer as insulative carpet and supported CNTs/GO thin film as conductive element have the potential application as flexible and miniature electric carpet for heating micro‐/nano devices locally.     

Additive Manufacturing of Engineered Living Materials with Bio-Augmented Mechanical Properties and Resistance to Degradation

Engineered living materials (ELMs) combine living cells with polymeric matrices to yield unique materials with programmable functions. While the cellular platform and the polymer network determine the material properties and applications, there are still gaps in the ability to seamlessly integrate the biotic (cellular) and abiotic (polymer) components into singular materials, then assemble them into devices and machines. Herein, the additive-manufacturing of ELMs wherein bioproduction of metabolites from the encapsulated cells enhanced the properties of the surrounding matrix is demonstrated. First, aqueous resins are developed comprising bovine serum albumin (BSA) and poly(ethylene glycol diacrylate) (PEGDA) with engineered microbes for vat photopolymerization to create objects with a wide array of 3D form factors. The BSA-PEGDA matrix afforded hydrogels that are mechanically stiff and tough for use in load-bearing applications. Second, the continuous in situ production of l -DOPA, naringenin, and betaxanthins from the engineered cells encapsulated within the BSA-PEGDA matrix is demonstrated. These microbial metabolites bioaugmented the properties of the BSA-PEGDA matrix by enhancing the stiffness (l -DOPA) or resistance to enzymatic degradation (betaxanthin). Finally, the assembly of the 3D printed ELM components into mechanically functional bolts and gears to showcase the potential to create functional ELMs for synthetic living machines is demonstrated.     

3D Printed Actuators: Reversibility,Relaxation, and Ratcheting

Additive manufacturing strives to combine any combination of materials into 3D functional structures and devices, ultimately opening up the possibility of 3D printed machines. It remains difficult to actuate such devices, thus limiting the scope of 3D printed machines to passive devices or necessitating the incorporation of external actuators that are manufactured differently. Here, 3D printed hybrid thermoplast/conducter bilayers are explored, which can be actuated by differential heating caused by externally controllable currents flowing through their conducting faces. The functionality of such actuators is uncovered and it is shown that they allow to 3D print, in one pass, simple flexible robotic structures that propel forward under step‐wise applied voltages. Moreover, exploiting the thermoplasticity of the nonconducting plastic parts at elevated temperatures, it is shown that how strong driving leads to irreversible deformations—a form of 4D printing—which also enlarges the range of linear response of the actuators. Finally, it is shown that how to leverage such thermoplastic relaxations to accumulate plastic deformations and obtain very large deformations by alternatively driving both layers of a bilayer; this is called ratcheting. The strategy is scalable and widely applicable, and opens up a new approach to reversible actuation and irreversible 4D printing of arbitrary structures and machines.     

基于 3D 打印的THz 波导成型技术研究进展

本文首先介绍了太赫兹波导和3D 打印技术的发展现状。3D 打印作为一项新兴的技术,以数字模型文件为基础, 运用粉末状金属或塑料等可粘合材料通过逐层打印的方法构造实体,打破了传统THz 波导技术的局限性。本文介绍的3D 打印THz 波导利用聚合树脂作为打印材料,打印完成的THz 波导在其传输通路上镀500nm 的金,金的厚度足以支持THz 传播。利用这种方法可以打印出直波导、三维弯曲面、三维Y 劈和U 型波导等多种结构。3D 打印THz 波导除传输损耗 略高外,其传输模式及其特性与传统的金属波导基本一致,这种额外的传输损耗归咎于商业3D 打印机的精度。     

3D Printed Microstructures Erasable by Darkness

To advance the applications of direct laser writing (DLW), adaptability of the printed structure is critical, prompting a shift toward printing structures that are comprised of different materials, and/or can be partially or fully erased on demand. However, most structures that contain these features are often printed by complex processes or require harsh developing techniques. Herein, a unique photoresist for DLW is introduced that is capable of printing 3D microstructures that can be erased by exposure to darkness. Specifically, microstructures based on light-stabilized dynamic materials are fabricated that remain stable when continously irradiated with green light, but degrade once the light source is switched off. The degradation and light stabilization properties of the printed materials are analyzed in-depth by time-lapse scanning electron microscopy. It is demonstrated that these resists can be used to impart responsive behavior onto the printed structure, and –critically– as a temporary locking mechanism to control the release of moving structural features.     

Design and calibration of 3D printed soft deformation sensors for soft actuator control

Soft actuators made from compliant materials are superior to conventional rigid robots in terms of flexibility, adaptability and safety. However, an inherent drawback of soft actuator is the low actuation precision. Implementing closed loop control is a possible solution, but the soft actuator shape can hardly be measured directly by commercially available sensors, which either are too stiff for integration or cause performance degradation of the actuator. Although 3D printing has been applied to print bendable sensors from conductive materials, they either have larger stiffness than the soft actuator or are made from specially designed materials that are difficult to reproduce. In this study, easily accessible commercial soft conductive material is applied to directly 3D print soft sensors on soft actuators. Different configurations of the printed sensors are studied to investigate how the sensor design affects the performance. The best sensor configuration is selected to provide shape feedback using its changing resistance during deformation. Compared with a commercial flexible bending sensor, the printed sensor has less influences on the soft actuator performance and enjoys higher shape estimation accuracy. Closed loop shape control of the actuator using feedback from the 3D printed sensor is then designed, implemented and compared with the control results using image feedback. A gripper consisting of three individually controlled soft actuators demonstrates the applications of the soft sensor.     

飞秒激光双光子聚合加工微纳结构

针对微/纳机电系统（MEMS/NEMS）零部件加工制造难题,研究具有亚衍射极限空间分辨率的飞秒激光双光子聚合加工方法,搭建钛蓝宝石飞秒激光微纳加工系统,对液态聚合物材料进行飞秒激光双光子聚合加工工艺试验研究。结果表明:随着激光功率的降低,单个固化点的尺寸减小,加工分辨率提高;扫描步距减小,所加工工件的表面粗糙度数值减小,但加工效率降低。基于CAD软件设计出微米墙和纳米线构成的三维微纳结构,利用飞秒激光双光子聚合加工得到该三维微纳结构实物,通过优化工艺参数加工出直径小于100 nm的纳米线,从而证明飞秒激光双光子聚合加工方法为微/纳器件的制造提供了一种有效方法。     

Diels–Alder Reversible Thermoset 3D Printing: Isotropic Thermoset Polymers via Fused Filament Fabrication

This study presents a new 3D printing process, the Diels–Alder reversible thermoset (DART) process, and a first generation of printable DART resins, which exhibit thermoset properties at use temperatures, ultralow melt viscosity at print temperatures, smooth part surface finish, and as‐printed isotropic mechanical properties. This study utilizes dynamic covalent chemistry based on reversible furan‐maleimide Diels–Alder linkages in the polymers, which can be decrosslinked and melt‐processed during printing between 90 and 150 °C, and recrosslinked at lower temperatures to their entropically favored state. This study compares the first generation of DART materials to commonly 3D printed high‐toughness thermoplastics. Parts printed from typical fused filament fabrication compatible materials exhibit anisotropy of more than 50% and sometimes upward of 98% in toughness when deformed along the build direction, while the first generation of DART materials exhibit less than 4% toughness reduction when deformed along the build direction. At room temperature, the toughest DART materials exhibit baseline toughness of 18.59 ± 0.91 and 18.36 ± 0.57 MJ m^?3 perpendicular and parallel to the build direction, respectively. DART printing will enable chemists, polymer engineers, materials scientists, and industrial designers to translate new robust materials possessing targeted thermomechanical properties, multiaxial toughness, smooth surface finish, and low anisotropy.     

3D Printing of a Thermo‐ and Solvatochromic Composite Material Based on a Cu(II)–Thymine Coordination Polymer with Moisture Sensing Capabilities

This work presents the fabrication of 3D‐printed composite objects based on copper(II) 1D coordination polymer ( CP1 ) decorated with thymine along its chains with potential utility as an environmental humidity sensor and as a water sensor in organic solvents. This new composite object has a remarkable sensitivity, ranging from 0.3% to 4% of water in organic solvents. The sensing capacity is related to the structural transformation due to the loss of water molecules that CP1 undergoes with temperature or by solvent molecules' competition, which induces significant change in color simultaneously. The CP1 and 3D printed materials are stable in air over 1 year and also at biological pHs (5–7), therefore suggesting potential applications as robust colorimetric sensors. These results open the door to generate a family of new 3D printed materials based on the integration of multifunctional coordination polymers with organic polymers.     

Additive Manufacturing of Porous Biominerals

Nature fabricates hard functional materials from soft organic scaffolds that are mineralized. To enable an energy-efficient locomotion of these creatures while maintaining their structural stability, nature often renders parts of these minerals porous. Unfortunately, methods to produce synthetic minerals with a similar degree of control over their multi length scale porous structure remain elusive. This level of control, however, would be required to design lightweight yet robust biominerals. Here, a room temperature process is presented that combines a localized mineralization with emulsion-based 3D printing to form cm sized biominerals possessing pores whose diameters range from the 100 s of nm up to the mm length scale. The samples encompass up to 80 wt% of CaCO₃ and display a specific compressive strength that is significantly higher than that of previously reported 3D printed porous biominerals and close to those of trabecular bones. The universality of this approach by forming different types of bioactive minerals, including calcite, aragonite, and brushite is demonstrated. The ability to 3D print these materials under benign conditions renders this energy-efficient process well-suited to construct cm-sized lightweight yet load-bearing structures that might find applications, for example, in the design of the next generation of flying or motile objects.     

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.     

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.     

Ionic Hydrogels with Biomimetic 4D‐Printed Mechanical Gradients: Models for Soft‐Bodied Aquatic Organisms

Direct‐ink writing (DIW), a rapidly growing and advancing form of additive manufacturing, provides capacities for on‐demand tailoring of materials to meet specific requirements for final designs. The penultimate challenge faced with the increasing demand of customization is to extend beyond modification of shape to create 4D structures, dynamic 3D structures that can respond to stimuli in the local environment. Patterning material gradients is foundational for assembly of 4D structures, however, there remains a general need for useful materials chemistries to generate gray scale gradients via DIW. Here, presented is a simple materials assembly paradigm using DIW to pattern ionotropic gradients in hydrogels. Using structures that architecturally mimic sea‐jelly organisms, the capabilities of spatial patterning are highlighted as exemplified by selectively programming the valency of the ion‐binding agents. Spatial gradients, when combined with geometry, allow for programming the flexibility and movement of iron oxide nanoparticle–loaded ionotropic hydrogels to generate 4D‐printed structures that actuate in the presence of local magnetic fields. This work highlights approaches to 4D design complexity that exploits 3D‐printed gray‐scale/gradient mechanics.     

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.     

Printing Hydrogels and Elastomers in Arbitrary Sequence with Strong Adhesion

Many recently demonstrated devices require the integration of hydrogels and hydrophobic elastomers. Extrusion print is a promising method for rapid prototyping but existing approaches do not fulfill a basic requirement: print integrated structures of a hydrogel and an elastomer, in arbitrary sequence, with strong adhesion. This paper demonstrates an approach to fulfill this requirement. During print, the ink of each material flows through a nozzle under a pressure gradient but retains the shape against gravity and capillarity. During cure, covalent bonds form to link monomer units into polymer chains, crosslink the polymer chains into the polymer networks of the hydrogel and the elastomer, as well as interlink the two polymer networks into an integrated structure. The approach covalently interlinks the hydrogel network and the elastomer network by adding an interlink initiator in one of the inks. An adhesion energy above 5000 J m^?2 is demonstrated. Printed morphing structures survive swelling and printed artificial axons survive repeated hits of a hammer. This approach opens a road to the development of soft devices for broad applications in medicine and engineering.     

Multi-Material 3D Microprinting of Magnetically Deformable Biocompatible Structures

Two-photon polymerization (2PP) allows precise 3D printing at the micrometer scale, and by associating it with magnetic materials, the creation of remotely actuatable micro-structures. Such structures attract a growing interest for biomedical applications, thanks to their size and to the biocompatibility of some photoresist materials. Gelatin methacryloyl (Gel-MA) is one such material, and can be used to create physiological scaffolds for cell culture. Here, the physico-chemical properties of two resins are exploited, the first being a silica-based hybrid polymer, the OrmoComp, and the second a Gel-MA-based hydrogel. A 2PP manufacturing protocol is defined and designed to print both materials in succession as a single structure, which is then linked to a neodymium-iron-boron (NdFeB) magnetic bead for actuation. By this combination, a magnetically deformable 3D culture substrate is created to study cells in an environment that mimics soft, curved, and dynamic properties of tissues in vivo. The structure is actuated via an external magnetic field and bends back and forth along its longest axis. Lastly, preliminary cell culture trials are conducted showing the proliferation of cells on the structures.     

New antenna design approach – 3D polymer printing and metallization. experimental test at 14–18 GHz

This paper proves a new approach for rapid prototyping of radio antennas through 3D printing and chemical metallization. For this purpose, a standard metal pyramidal horn prototype is compared with its 3D printed replica. Three different 3D polymer printers are tested. The printed samples are assessed nondestructively by an X-ray Industrial Computed Tomography (CT) scanner, and then metalized via chemical deposition and chemical-electrochemical deposition. Copper with two different layer thicknesses and nickel materials are deployed and verified as a metallization opportunity. Again the CT scanner, X-ray fluorescent analysis and nanoindentation technique were used to perform the metallization quality estimation. As a result, a qualitative polymer prototype was produced having weight of 13 g – ten times lighter than the original. The prototype was successfully metalized and was able to be soldered. The radio-measurement comparison with the metal original for frequencies 14–18 GHz showed no significant differences. Finally, a simple dynamometric test confirmed the bonding between the metal and the polymer. To the best of our knowledge this is the first known comprehensive analysis of the possibility to print 3D lightweight wideband polymer antenna prototypes with a stable chemical metallization and radio properties very close to the original at 14–18 GHz.     

Bioinspired Electro‐Thermo‐Hygro Reversible Shape‐Changing Materials by 4D Printing

Hygromorph composites are moisture‐induced shape‐changing materials that are increasingly studied to develop autonomously actuated deployable structures. The morphing mechanism is based on the high affinity for moisture and the hygroexpansive nature of at least one component, combined with a bilayer microstructure. Among available hygromorphs, those consisting of cellulosic or hydrogel material‐based actuators trigger fast responses to moisture. Their stiffness however decreases significantly with the moisture content and that restricts their potential application as soft actuators. This work proposes a novel 4D printed multistimuli‐responsive structural material based on conductive carbon reinforcements and combined with a moisture sensitive polymer. These 4D printed materials possess a microstructure that provides the capability of natural actuators like pine cones. The actuation of these functional materials could be either triggered passively by the variation of the ambient moisture, or by electroheating, with the latter leading to the control of the moisture content in initially wet samples via Joule effects. This new class of functional materials shows an increase of the actuation speed by a factor 10 compared to other existing hygromorphs with the same responsiveness. When the electrical heating is turned off, passive cooling and moisture driven actuation is triggered in a full reversible mode.     

Acrylate‐Based Photopolymer for Two‐Photon Microfabrication and Photonic Applications

This paper provides a photopolymerizing material suitable for stereolithography of complex submicrometer‐sized three‐dimensional (3D) structural elements to a broad scientific public. Here, we present the formulation of a polymer (LN1 resin) that allows further research in the field of nanofabrication and ‐technology as it surpasses current material limitations. The polymer consists of multifunctional acrylate oligomers as binder, polyfunctional monomers, and a photoinitiator (PI). The chemistry to form 3D structures is based on photopolymerization of the acrylate system initiated by free‐radical species that are triggered by two‐photon absorption of a PI. Important parameters of photocuring, such as the effects of PI concentration, temperature, and light intensity, were studied using photocalorimetry. The thermal stability of the material was tested using thermal gravimetric analysis, providing key information for electronic and photonic applications. Photonic‐crystal structures generated from this resin exhibiting photonic stop gaps in near‐infrared‐ and telecommunication‐wavelength regions are presented.