Gravity Drawing of Micro‐ and Nanofibers for Additive Manufacturing of Well‐Organized 3D‐Nanostructured Scaffolds

This work introduces a gravity fiber drawing (GFD) method of making single filament nanofibers from polymer solutions and precise alignment of the fibers in 3D scaffolds. This method is advantageous for nanofiber 3D alignment in contrast to other known methods. GFD provides a technology for the fabrication of freestanding filament nanofibers of well‐controlled diameter, draw ratio, and 3D organization with controllable spacing and angular orientation between nanofibers. The GFD method is capable of fabricating complex 3D scaffolds combining fibers with different diameters, chemical compositions, mechanical properties, angular orientations, and multilayer structures in the same construct. The scaffold porosity can be as high as 99% to secure transport of nutrients and space for cell infiltration and differentiation in tissue engineering and 3D cell culture applications.     

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.     

Engineering 2D Mesoporous Silica@MXene‐Integrated 3D‐Printing Scaffolds for Combinatory Osteosarcoma Therapy and NO‐Augmented Bone Regeneration

The rising concerns of the recurrence and bone deficiency in surgical treatment of malignant bone tumors have raised an urgent need of the advance of multifunctional therapeutic platforms for efficient tumor therapy and bone regeneration. Herein, the construction of a multifunctional biomaterial system is reported by the integration of 2D Nb₂C MXene wrapped with S‐nitrosothiol (R? SNO)‐grafted mesoporous silica with 3D‐printing bioactive glass (BG) scaffolds (MBS). The near infrared (NIR)‐triggered photonic hyperthermia of MXene in the NIR‐II biowindow and precisely controlled nitric oxide (NO) release are coordinated for multitarget ablation of bone tumors to enhance localized osteosarcoma treatment. The in situ formed phosphorus and calcium components degraded from BG scaffold promote bone‐regeneration bioactivity, augmented by sufficient blood supply triggered by on‐demand NO release. The tunable NO generation plays a crucial role in sequential adjuvant tumor ablation, combinatory promotion of coupled vascularization, and bone regeneration. This study demonstrates a combinatory osteosarcoma ablation and a full osseous regeneration as enabled by the implantation of MBS. The design of multifunctional scaffolds with the specific features of controllable NO release, highly efficient photothermal conversion, and stimulatory bone regeneration provides an intriguing biomaterial platform for the diversified treatment of bone tumors.     

3D‐Printing Electrolytes for Solid‐State Batteries

Solid‐state batteries have many enticing advantages in terms of safety and stability, but the solid electrolytes upon which these batteries are based typically lead to high cell resistance. Both components of the resistance (interfacial, due to poor contact with electrolytes, and bulk, due to a thick electrolyte) are a result of the rudimentary manufacturing capabilities that exist for solid‐state electrolytes. In general, solid electrolytes are studied as flat pellets with planar interfaces, which minimizes interfacial contact area. Here, multiple ink formulations are developed that enable 3D printing of unique solid electrolyte microstructures with varying properties. These inks are used to 3D‐print a variety of patterns, which are then sintered to reveal thin, nonplanar, intricate architectures composed only of Li₇La₃Zr₂O₁₂ solid electrolyte. Using these 3D‐printing ink formulations to further study and optimize electrolyte structure could lead to solid‐state batteries with dramatically lower full cell resistance and higher energy and power density. In addition, the reported ink compositions could be used as a model recipe for other solid electrolyte or ceramic inks, perhaps enabling 3D printing in related fields.     

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.     

Additive Manufacturing of 3D‐Architected Multifunctional Metal Oxides

Additive manufacturing (AM) of complex three‐dimensional (3D) metal oxides at the micro‐ and nanoscales has attracted considerable attention in recent years. State‐of‐the‐art techniques that use slurry‐based or organic–inorganic photoresins are often hampered by challenges in resin preparation and synthesis, and/or by the limited resolution of patterned features. A facile process for fabricating 3D‐architected metal oxides via the use of an aqueous metal‐ion‐containing photoresin is presented. The efficacy of this process, which is termed photopolymer complex synthesis, is demonstrated by creating nanoarchitected zinc oxide (ZnO) architectures with feature sizes of 250 nm, by first patterning a zinc‐ion‐containing aqueous photoresin using two‐photon lithography and subsequently calcining them at 500 ºC. Transmission electron microscopy (TEM) analysis reveals their microstructure to be nanocrystalline ZnO with grain sizes of 5.1 ± 1.6 nm. In situ compression experiments conducted in a scanning electron microscope show an emergent electromechanical response: a 200 nm mechanical compression of an architected ZnO structure results in a voltage drop of 0.52 mV. This photopolymer complex synthesis provides a pathway to easily create arbitrarily shaped 3D metal oxides that could enable previously impossible devices and smart materials.     

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.     

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‐Printable Photochromic Molecular Materials for Reversible Information Storage

The formulation of advanced molecular materials with bespoke polymeric ionic‐liquid matrices that stabilize and solubilize hybrid organic–inorganic polyoxometalates and allow their processing by additive manufacturing, is effectively demonstrated. The unique photo and redox properties of nanostructured polyoxometalates are translated across the scales (from molecular design to functional materials) to yield macroscopic functional devices with reversible photochromism. These properties open a range of potential applications including reversible information storage based on controlled topological and temporal reduction/oxidation of pre‐formed printed devices. This approach pushes the boundaries of 3D printing to the molecular limits, allowing the freedom of design enabled by 3D printing to be coupled with the molecular tuneability of polymerizable ionic liquids and the photoactivity and orbital engineering possible with hybrid polyoxometalates.     

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.     

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.     

3D‐Structured Stretchable Strain Sensors for Out‐of‐Plane Force Detection

Stretchable strain sensors, as the soft mechanical interface, provide the key mechanical information of the systems for healthcare monitoring, rehabilitation assistance, soft exoskeletal devices, and soft robotics. Stretchable strain sensors based on 2D flat film have been widely developed to monitor the in‐plane force applied within the plane where the sensor is placed. However, to comprehensively obtain the mechanical feedback, the capability to detect the out‐of‐plane force, caused by the interaction outside of the plane where the senor is located, is needed. Herein, a 3D‐structured stretchable strain sensor is reported to monitor the out‐of‐plane force by employing 3D printing in conjunction with out‐of‐plane capillary force‐assisted self‐pinning of carbon nanotubes. The 3D‐structured sensor possesses large stretchability, multistrain detection, and strain‐direction recognition by one single sensor. It is demonstrated that out‐of‐plane forces induced by the air/fluid flow are reliably monitored and intricate flow details are clearly recorded. The development opens up for the exploration of next‐generation 3D stretchable sensors for electronic skin and soft robotics.