3D‐Printed Transparent Glass

Silica inks are developed, which may be 3D printed and thermally processed to produce optically transparent glass structures with sub‐millimeter features in forms ranging from scaffolds to monoliths. The inks are composed of silica powder suspended in a liquid and are printed using direct ink writing. The printed structures are then dried and sintered at temperatures well below the silica melting point to form amorphous, solid, transparent glass structures. This technique enables the mold‐free formation of transparent glass structures previously inaccessible using conventional glass fabrication processes.     

2D‐Black‐Phosphorus‐Reinforced 3D‐Printed Scaffolds:A Stepwise Countermeasure for Osteosarcoma

With the ever‐deeper understanding of nano–bio interactions and the development of fabrication methodologies of nanomaterials, various therapeutic platforms based on nanomaterials have been developed for next‐generation oncological applications, such as osteosarcoma therapy. In this work, a black phosphorus (BP) reinforced 3D‐printed scaffold is designed and prepared to provide a feasible countermeasure for the efficient localized treatment of osteosarcoma. The in situ phosphorus‐driven, calcium‐extracted biomineralization of the intra‐scaffold BP nanosheets enables both photothermal ablation of osteosarcoma and the subsequent material‐guided bone regeneration in physiological microenvironment, and in the meantime endows the scaffolds with unique physicochemical properties favoring the whole stepwise therapeutic process. Additionally, a corrugated structure analogous to Haversian canals is found on newborn cranial bone tissue of Sprague–Dawley rats, which may provide much inspiration for the future research of bone‐tissue engineering.     

Laminated Object Manufacturing of 3D‐Printed Laser‐Induced Graphene Foams

Laser‐induced graphene (LIG), a graphene structure synthesized by a one‐step process through laser treatment of commercial polyimide (PI) film in an ambient atmosphere, has been shown to be a versatile material in applications ranging from energy storage to water treatment. However, the process as developed produces only a 2D product on the PI substrate. Here, a 3D LIG foam printing process is developed on the basis of laminated object manufacturing, a widely used additive‐manufacturing technique. A subtractive laser‐milling process to yield further refinements to the 3D structures is also developed and shown here. By combining both techniques, various 3D graphene objects are printed. The LIG foams show good electrical conductivity and mechanical strength, as well as viability in various energy storage and flexible electronic sensor applications.     

Shaping Giant Membrane Vesicles in 3D‐Printed Protein Hydrogel Cages

Giant unilamellar phospholipid vesicles are attractive starting points for constructing minimal living cells from the bottom‐up. Their membranes are compatible with many physiologically functional modules and act as selective barriers, while retaining a high morphological flexibility. However, their spherical shape renders them rather inappropriate to study phenomena that are based on distinct cell shape and polarity, such as cell division. Here, a microscale device based on 3D printed protein hydrogel is introduced to induce pH‐stimulated reversible shape changes in trapped vesicles without compromising their free‐standing membranes. Deformations of spheres to at least twice their aspect ratio, but also toward unusual quadratic or triangular shapes can be accomplished. Mechanical force induced by the cages to phase‐separated membrane vesicles can lead to spontaneous shape deformations, from the recurrent formation of dumbbells with curved necks between domains to full budding of membrane domains as separate vesicles. Moreover, shape‐tunable vesicles are particularly desirable when reconstituting geometry‐sensitive protein networks, such as reaction‐diffusion systems. In particular, vesicle shape changes allow to switch between different modes of self‐organized protein oscillations within, and thus, to influence reaction networks directly by external mechanical cues.     

Thermal Shock Synthesis of Nanocatalyst by 3D‐Printed Miniaturized Reactors

High temperature synthesis and treatments are ubiquitous in chemical reactions and material manufacturing. However, conventional sintering furnaces are bulky and inefficient with a narrow temperature range (<1500 K) and slow heating rates (<100 K min^?1), which are undesirable for many applications that require transient heating to produce ideal nanostructures. Herein, a 3D‐printed, miniaturized reactor featuring a dense micro‐grid design is developed to maximize the material contact and therefore acheive highly efficient and controllable heating. By 3D printing, a versatile, miniaturized reactor with microscale features can be constructed, which can reach a much wider temperature range (up to ≈3000 K) with ultrafast heating/cooling rates of ≈10⁴ K s^?1. To demonstrate the utility of the design, rapid and batch synthesis of Ru nanoparticles supported in ordered mesoporous carbon is performed by transient heating (1500 K, 500 ms). The resulting ultrafine and uniform Ru nanoparticles (≈2 nm) can serve as a cathode in Li‐CO₂ batteries with good cycling stability. The miniaturized reactor, with versatile shape design and highly controllable heating capabilities, provides a platform for nanocatalyst synthesis with localized and ultrafast heating toward high temperatures that is otherwise challenging to achieve.     

3D‐Printed Scanning‐Probe Microscopes with Integrated Optical Actuation and Read‐Out

Scanning‐probe microscopy (SPM) is the method of choice for high‐resolution imaging of surfaces in science and industry. However, SPM systems are still considered as rather complex and costly scientific instruments, realized by delicate combinations of microscopic cantilevers, nanoscopic tips, and macroscopic read‐out units that require high‐precision alignment prior to use. This study introduces a concept of ultra‐compact SPM engines that combine cantilevers, tips, and a wide variety of actuator and read‐out elements into one single monolithic structure. The devices are fabricated by multiphoton laser lithography as it is a particularly flexible and accurate additive nanofabrication technique. The resulting SPM engines are operated by optical actuation and read‐out without manual alignment of individual components. The viability of the concept is demonstrated in a series of experiments that range from atomic‐force microscopy engines offering atomic step height resolution, their operation in fluids, and to 3D printed scanning near‐field optical microscopy. The presented approach is amenable to wafer‐scale mass fabrication of SPM arrays and capable to unlock a wide range of novel applications that are inaccessible by current approaches to build SPMs.     

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.     

Out‐of‐Plane 3D‐Printed Microfibers Improve the Shear Properties of Hydrogel Composites

One challenge in biofabrication is to fabricate a matrix that is soft enough to elicit optimal cell behavior while possessing the strength required to withstand the mechanical load that the matrix is subjected to once implanted in the body. Here, melt electrowriting (MEW) is used to direct‐write poly(ε‐caprolactone) fibers “out‐of‐plane” by design. These out‐of‐plane fibers are specifically intended to stabilize an existing structure and subsequently improve the shear modulus of hydrogel–fiber composites. The stabilizing fibers (diameter = 13.3 ± 0.3 µm) are sinusoidally direct‐written over an existing MEW wall‐like structure (330 µm height). The printed constructs are embedded in different hydrogels (5, 10, and 15 wt% polyacrylamide; 65% poly(2‐hydroxyethyl methacrylate) (pHEMA)) and a frequency sweep test (0.05–500 rad s^?1, 0.01% strain, n = 5) is performed to measure the complex shear modulus. For the rheological measurements, stabilizing fibers are deposited with a radial‐architecture prior to embedding to correspond to the direction of the stabilizing fibers with the loading of the rheometer. Stabilizing fibers increase the complex shear modulus irrespective of the percentage of gel or crosslinking density. The capacity of MEW to produce well‐defined out‐of‐plane fibers and the ability to increase the shear properties of fiber‐reinforced hydrogel composites are highlighted.     

Novel 3D‐Printed Hybrid Auxetic Mechanical Metamaterial with Chirality‐Induced Sequential Cell Opening Mechanisms

New hybrid auxetic chiral mechanical metamaterial are designed and fabricated via multi‐material 3D printing. Due to the chirality‐induced rotation, the material have unique sequential cell‐opening mechanisms. Mechanical experiments on the 3D printed prototypes and systematic FE simulations show that the effective stiffness, the Poisson's ratio and the cell‐opening mechanisms of the new design can be tuned in a very wide range by tailoring two non‐dimensional parameters: the cell size ratio and stiffness ratio of component materials. As example applications, sequential particle release mechanisms and color changing mechanisms of the new designs are also systematically explored. The present new design concepts can be used to develop new multi‐functional smart composites, sensors and/or actuators which are responsive to external load and/or environmental conditions for applications in drug delivery and color changing for camouflage.

     

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.     

Smartdust 3D‐Printed Graphene‐Based Al/Ga Robots for Photocatalytic Degradation of Explosives

Milli/micro/nanorobots are considered smart devices able to convert energy taken from different sources into mechanical movement and accomplish the appointed tasks. Future advances and realization of these tiny devices are mostly limited by the narrow window of material choices, the fuel requirement, multistep surface functionalization, rational structural design, and propulsion ability in complex environments. All these aspects call for intensive improvements that may speed up the real application of such miniaturized robots. 3D‐printed graphene‐based smartdust robots provided with a magnetic response and filled with aluminum/gallium molten alloy (Al/Ga) for autonomous motion are presented. These robots can swim by reacting with the surrounding environment without adding any fuel. Because their outer surface is coated with a hydrogel/photocatalyst (chitosan/carbon nitride, C₃N₄) layer, these robots are used for the photocatalytic degradation of the picric acid as an explosive model molecule under visible light. The results show a fast and efficient degradation of picric acid that is attributed to a synergistic effect between the adsorption capability of the chitosan and the photocatalytic activity of C₃N₄ particles. This work provides added insight into the large‐scale fabrication, easy functionalization, and propulsion of tiny robots for environmental applications.