High-performance polymers are an important class of materials that are used in challenging conditions, such as in aerospace applications. Until now, 3D printing based on stereolithography processes can not be performed due to a lack of suitable materials. There is report on new materials and printing compositions that enable 3D printing of objects having extremely high thermal resistance, with Tg of 283 °C and excellent mechanical properties. The printing is performed by a low-cost Digital Light Processing printer, and the formulation is based on a dual-cure mechanism, photo, and thermal process. The main components are a molecule that has both epoxy and acrylate groups, alkylated melamine that enables a high degree of crosslinking, and a soluble precursor of silica. The resulting objects are made of hybrid materials, in which the silicon is present in the polymeric backbone and partly as silica enforcement particles.

Photoelectrochemical water splitting is one of the sustainable routes to renewable hydrogen production. One of the challenges to deploying photoelectrochemical (PEC) based electrolyzers is the difficulty in the effective capture of solar radiation as the illumination angle changes throughout the day. Herein, we demonstrate a method for the angle-independent capture of solar irradiation by using transparent 3 dimensional (3D) lattice structures as the photoanode in PEC water splitting. The transparent 3D lattice structures were fabricated by 3D printing a silica sol-gel followed by aging and sintering. These transparent 3D lattice structures were coated with a conductive indium tin oxide (ITO) thin film and a Mo-doped BiVO4 photoanode thin film by dip coating. The sheet resistance of the conductive lattice structures can reach as low as 340 Ohms per sq for \~82% optical transmission. The 3D lattice structures furnished large volumetric current densities of 1.39 mA cm-3 which is about 2.4 times higher than a flat glass substrate (0.58 mA cm-3) at 1.23 V and 1.5 G illumination. Further, the 3D lattice structures showed no significant loss in performance due to a change in the angle of illumination, whereas the performance of the flat glass substrate was significantly affected. This work opens a new paradigm for more effective capture of solar radiation that will increase the solar to energy conversion efficiency.

Wearable electronics is an emerging field in academics and industry, in which electronic devices, such as smartwatches and sensors, are printed or embedded within textiles. The electrical circuits in electronics textile (e-textile) should withstand many cycles of bending and stretching. Direct printing of conductive inks enables the patterning of electrical circuits; however, while using conventional nanoparticle-based inks, printing onto the fabric results in a thin layer of a conductor, which is not sufficiently robust and impairs the reliability required for practical applications. Here, we present a new process for fabricating robust stretchable e-textile using a thermodynamically stable, solution-based copper complex ink, which is capable of full penetrating the fabric. After printing on knitted stretchable fabrics, they were heated, and the complex underwent an intermolecular self-reduction reaction. The continuously formed metallic copper was used as a seed layer for electroless plating (EP) to form highly conductive circuits. It was found that the stretching direction has a significant role in resistivity. This new approach enables fabricating e-textiles with high stretchability and durability, as demonstrated for wearable gloves, toward printing functional e-textile.

The use of conductive materials to be printed/embedded onto/within a polymeric matrix has gained increasing attention in the fabrication of next-generation soft electronics. In this review, we provide a comprehensive overview of the materials and approaches for the fabrication of 2D and 3D conductive structures while focusing on the importance of the compatibility between the particles' shape, the polymeric matrix type, and the deposition method, along with the target application. The review presents a summary of the main conductive materials and the type of polymeric materials which were utilized for fabricating soft electronic devices that are bendable/twistable and stretchable. It is divided into two sections: Introduction section, which presents briefly conductive materials, polymeric matrix, and fabrication methods, and Fabrication section, presenting the main 6 approaches of fabrication. Each of the fabrication subsections presents the main recent reports in a detailed table. The review is concluded with an Outlook section, describing the current challenges in this field. Despite the progress in the fabrication of 2D bendable/twistable electronic devices toward industrial integration, there is still a need for tailoring and improving the durability and robustness of 3D stretchable electronic devices.

Abstract Although natural continuum structures, such as the boneless elephant trunk, provide inspiration for new versatile grippers, highly deformable, jointless, and multidimensional actuation has still not been achieved. The challenging pivotal requisites are to avoid sudden changes in stiffness, combined with the capability of providing reliable large deformations in different directions. This research addresses these two challenges by harnessing porosity at two levels: material and design. Based on the extraordinary extensibility and compressibility of volumetrically tessellated structures with microporous elastic polymer walls, monolithic soft actuators are fabricated by 3D printing unique polymerizable emulsions. The resulting monolithic pneumatic actuators are printed in a single process and are capable of bidirectional movements with just one actuation source. The proposed approach is demonstrated by two proof-of-concepts: a three-fingered gripper, and the first ever soft continuum actuator that encodes biaxial motion and bidirectional bending. The results open up new design paradigms for continuum soft robots with bioinspired behavior based on reliable and robust multidimensional motions.

Humans rely increasingly on sensors to address grand challenges and to improve quality of life in the era of digitalization and big data. For ubiquitous sensing, flexible sensors are developed to overcome the limitations of conventional rigid counterparts. Despite rapid advancement in bench-side research over the last decade, the market adoption of flexible sensors remains limited. To ease and to expedite their deployment, here, we identify bottlenecks hindering the maturation of flexible sensors and propose promising solutions. We first analyze challenges in achieving satisfactory sensing performance for real-world applications and then summarize issues in compatible sensor-biology interfaces, followed by brief discussions on powering and connecting sensor networks. Issues en route to commercialization and for sustainable growth of the sector are also analyzed, highlighting environmental concerns and emphasizing nontechnical issues such as business, regulatory, and ethical considerations. Additionally, we look at future intelligent flexible sensors. In proposing a comprehensive roadmap, we hope to steer research efforts towards common goals and to guide coordinated development strategies from disparate communities. Through such collaborative efforts, scientific breakthroughs can be made sooner and capitalized for the betterment of humanity.

[4 + 4] and [2 + 2] cycloadditions are unique reactions since they form and deform cycloadducts under irradiation due to their inherent reversible nature. Whereas promising for the field of recycling, these reactions usually suffer from two major shortcomings: long reaction durations (hours) and the requirement of high-intensity light (\~100 W/cm2), typically at a short wavelength (<330 nm). We demonstrate several tetra-dentate catalysts that can overcome these fundamental limitations. Among them is a tin complex that enables 76% conversion within only 2 min of irradiation at 395 nm, much faster than the known ruthenium-based catalyst, under irradiation with light intensity two orders of magnitude lower than that reported in the literature. Due to the short photopolymerization time, low intensity (27 mW/cm2), and long UV light (395 nm), this unique complex opens new avenues for recycling three-dimensional printing products based on photopolymerization of cycloaddition reactions.

We describe a new process for fabricating chiral organosilica 3D complex structures by combining digital light processing 3D printing with a sol-gel polycondensation process. The fabricated low-density objects have a high surface area with hierarchical porosity based on micropores resulting from the materials' design, and on macropores in the structure resulting from the 3D printing design. Thus, several 3D objects having complex shapes were printed by the polycondensation of 3-acryloxypropyltrimethoxysilane (APTMS) and chiral silane monomers that were obtained by reacting (1R,2R)-cyclohexane-1,2-diamine or (1S,2S)-cyclohexane-1,2-diamine with (3-Isocyanatopropyl)triethoxysilane. The dual-function monomer APTMS enabled both localized photopolymerization and polycondensation. Printed gyroids, cubes, and disk-shaped chiral monoliths successfully revealed the enantioselective adsorption of tryptophan enantiomers. It was found that the macroscopic shape of the monolith affects the adsorption performance and its enantioselectivity. High enantioselectivity was obtained when the objects were formed from a chiral silane synthesized from (1R,2R)-cyclohexane-1,2-diamine: L-tryptophan was adsorbed ∼10 fold higher than D-tryptophan. When the chiral object was fabricated using a chiral silane monomer prepared from (1S,2S)-cyclohexane-1,2-diamine, the enantioselectivity of the adsorption was reversed towards the D-tryptophan isomer. The new approach utilizes the 3D printing methodologies developed here for all-printed enantioselective separation columns; the printed macroporosity facilitates efficient flow, and the meso/microporous walls facilitate enantioselectivity.

4D printing is based on 3D printing of objects that can change their shape upon a proper triggering. Here, a novel approach is reported for fabricating programmable 3D printed objects composed of shape-memory polymers (SMPs) that are activated by light. The light activation of the movement and shape morphing are based on combining gold nanoparticles (AuNPs) as photothermal converters with acrylate-based printing compositions that form an SMP with tunable transition temperatures. The shape change of the printed objects is triggered by remote irradiation with a low-cost LED light at a wavelength specific to the surface plasmon resonance of the embedded AuNPs. The light is converted to heat which enables the shape transition when the temperature reaches the Tg of the polymer. Excellent SMP properties are achieved with shape fixity and recovery ratios over 95%. This material composition and triggering approach enable fabricating programmable light-activated 3D printed structures with a dual transition while tuning the concentration. Furthermore, numerical simulations performed by finite-element analysis result in the excellent prediction of the shape-memory recovery. The presented approach can be applied in remotely controlling morphing, mainly for applications in the fields of actuators and soft robotics.

Smart windows are used to minimize overall indoor energy consumption for thermal regulation through the modulation of radiant and conducted heat. While the control of thermal radiation can be done effectively by various technologies such as electrochromic, thermochromic, photochromic, etc., the modulation of heat conduction through smart windows remains a very challenging problem to be solved. The main obstacles are the lack of an effective conduction pathway within a double-glazed window and the need for a reliable active thermal switching mechanism. In this work, we introduce a novel idea for modulating heat conduction through a smart window by building thermally conductive pathways via coatings together with a heat transfer switching channel. The thermal switch uses various FexOy-decorated carbon-based nanomaterials that can be turned `ON' or `OFF', thus modulating heat conduction through a window. By applying an external magnetic force, such carbon-based magnetic nanomaterials can be easily moved or aligned within the switching channel to modulate thermal conduction. In this work, FexOy-decorated carbon nanotubes (CNTs) and graphene are developed as a thermal conduction pathway, and a thermal heat switching mechanism is developed and proposed. The FexOy-decorated carbon nanotubes (CNTs) and graphene show excellent heat diffusivity as a thermal conduction pathway coating, through a 2 mm channel gap with a 40 mm distance from the heat source, whilst the thermal conduction switch proposed is shown to effectively modulate thermal conduction through it.

The use of conductive materials to be printed/embedded onto/within a polymeric matrix has gained increasing attention in the fabrication of next-generation soft electronics. In this review, we provide a comprehensive overview of the materials and approaches for the fabrication of 2D and 3D conductive structures while focusing on the importance of the compatibility between the particles’ shape, the polymeric matrix type, and the deposition method, along with the target application. The review presents a summary of the main conductive materials and the type of polymeric materials which were utilized for fabricating soft electronic devices that are bendable/twistable and stretchable. It is divided into two sections: Introduction section, which presents briefly conductive materials, polymeric matrix, and fabrication methods, and Fabrication section, presenting the main 6 approaches of fabrication. Each of the fabrication subsections presents the main recent reports in a detailed table. The review is concluded with an Outlook section, describing the current challenges in this field. Despite the progress in the fabrication of 2D bendable/twistable electronic devices toward industrial integration, there is still a need for tailoring and improving the durability and robustness of 3D stretchable electronic devices.

The review is focused on bimetallic nanoparticles composed of a core formed by low-cost metal having high electrical conductivity, such as Cu and Ni, and a protective shell composed of stable to oxidation noble metal such as Ag or Au. We present the chemical and physical approaches for synthesis of such particles, as well as the combination of the two, the stability to oxidation of core-shell nanoparticles at various conditions, and the formulation of conductive compositions and their application in conductive coatings and printed electronics.

The application of flexible indium tin oxide (ITO)-free electrochromic devices (FCDs) has always been a research hotspot in flexible electronics. Recently, a silver nanowire (AgNW)-based transparent conductive film has raised great interest as an ITO-free substrate for FCDs. However, several challenges, such as the weak binding of AgNWs to the substrate, high junction resistance, and oxidation of AgNWs, remain. In this paper, a novel method for surface modification of AgNWs with N-aminoethyl-γ-aminopropyltrimethoxysilane [Si(NH2)] solution is proposed to enhance the bonding with the flexible substrates and the active materials, thereby inhibiting the delamination of AgNWs from the substrate and reducing the high junction resistance between nanowires. The TiO2/AgNW-Si(NH2)/poly(ethylene terephthalate) (PET) films show outstanding mechanical properties, of which the resistance remains almost unchanged after mechanical bending of 5000 cycles (R/R0 3.6%) and repeated peeling off cycles with 3M tape 100 times (R/R0 6.0%). In addition, we found that the oxygen-containing groups on the TiO2/AgNW-Si(NH2)/PET surface form hydrogen bonds with the TiO2 sol, resulting in tight contact between the TiO2 sol and the AgNWs, which prevents the AgNWs from oxidation. As a result, the TiO2/AgNW-Si(NH2)/PET film exhibited long-time aging (R/R0 4.9% in the air for 100 days) stability. A FCD was constructed with the TiO2/AgNW-Si(NH2)/PET film, which showed excellent electrochromic performance (94% retention) after 5000 bending cycles, indicating high stability and mechanical flexibility. These results present a promising solution to the transparent conductive films for flexible energy devices.

Soft-tissue replacements are challenging due to the stringent compliance requirements for the implanted materials in terms of biocompatibility, durability, high wear resistance, low friction, and water content. Acrylate hydrogels are worth considering as soft tissue implants as they can be photocurable and sustain customized shapes through 3D bioprinting. However, acrylate-based hydrogels present weak mechanical properties and significant dimensional changes when immersed in liquids. To address these obstacles, we fabricated double network (DN) hydrogels composed of polyacrylic acid (PAA) and bacterial cellulose nanofibers (BCNFs) by one fast UV photopolymerization step. BCNFs/PAA hydrogels with a 0.5 wt% BCNFs content present an increased stiffness and a lower, non-pH-dependent swelling than PAA hydrogels or PAA hydrogels with cellulose nanocrystals. Besides, BCNFs/PAA hydrogels are biocompatible and can be frozen/thawed. Those characteristics endorse these hybrid hydrogels as potential candidates for vascular and cartilage tissue implants.

Tungsten, an essential refractory metal material, has the characteristics of high melting and boiling points, high hardness, low expansion coefficient, and low vapor pressure. An indirect strategy to print three-dimensional (3D) refractory metal materials via digital light processing (DLP) followed by a post-treatment process was proposed. To analyze this strategy, a transparent ink with tungsten salts was developed, printed into a 3D precursor via DLP, and subsequently transited into 3D porous tungsten. The ultraviolet rheological properties and stability of the ink, transition process from the precursor to a 3D article, and the properties of the obtained 3D porous tungsten were investigated. This ink was preferable for DLP 3D printing, possessing consistency, stability and favorable absorbance at the wavelength of 385 nm. With increasing temperature, the weight of the tungsten salt in the 3D precursor decreased by 8.97% and was transited to tungsten oxide below 460 °C, reduced to pure nano-sized tungsten at approximately 700 °C, and finally sintered into porous articles. The organics initially contributed to polymerization during printing as well as reduction as a carbon reducer after pyrolysis. The pore size distribution of porous tungsten is nonlinear or multimodal, depending on the final sintering temperature. At 1200 °C, two distinct peaks are observed in the pore distribution curves of the products. At 1400 °C, the small pore as a whole decreases from approximately 100-1000 nm. Correspondingly, the relative density of the samples increased with temperature.

Two-dimensional (2D) porous carbon-based composite nanosheets loaded with metal oxide nanoclusters are expected to be promising electrocatalysts for high-performance electrochemical sensors. However, for this complicated composite material, strict reaction conditions and complex synthesis steps limit its general application in electrochemical detection. Here we present a facile method to fabricate 2D mesoporous nitrogen-rich carbon nanosheets loaded with CeO2 nanoclusters (2D-mNC@CeO2), for fabricating superoxide anions (O2•−) electrochemical sensor. The method is based on block copolymers self-assembly and the affinity of polydopamine to metal ions to obtain organic-inorganic hybrid, which can be directly converted into 2D-mNC@CeO2 through carbonization strategy without structural deterioration. Characterizations demonstrate that the 2D-mNC@CeO2 owned the 2D N-doped carbon structure with an interlinked hierarchical mesoporous and the uniformly dispersed CeO2 nanoclusters on the surface. Benefitted from the unique structure, the 2D-mNC@CeO2 shortens electron transfer distance, enhances mass transfer efficiency, exposes numerous active sites, and obtain a high Ce3+/Ce4+ ratio for improving electrocatalytic performance. The 2D-mNC@CeO2/SPCEs sensors for O2•− detection has a detection limit of 0.179 μM (S/N = 3) and sensitivity of 401.4 μA cm-2 mM-1. The sensors can be applied to capture electrochemical signals of O2•− released from HepG2 cells, demonstrating the application potential of the sensors to monitor O2•− in biological fields.

Wood warping is a phenomenon known as a deformation in wood that occurs when changes in moisture content cause an unevenly volumetric change due to fiber orientation. Here we present an investigation of wood warped objects that were fabricated by 3D printing. Similar to natural wood warping, water evaporation causes volume decrease of the printed object, but in contrast, the printing pathway pattern and flow rate dictate the direction of the alignment and its intensity, all of which can be predesigned and affect the resulting structure after drying. The fabrication of the objects was performed by an extrusion-based 3D printing technique that enables the deposition of water-based inks into 3D objects. The printing ink was composed of 100% wood-based materials, wood flour, and plant-extracted natural binders cellulose nanocrystals, and xyloglucan, without the need for any additional synthetic resins. Two archetypal structures were printed: cylindrical structure and helices. In the former, we identified a new length scale that gauges the effect of gravity on the shape. In the latter, the structure exhibited a shape transition analogous to the opening of a seedpod, quantitatively reproducing theoretical predictions. Together, by carefully tuning the flow rate and printing pathway, the morphology of the fully dried wooden objects can be controlled. Hence, it is possible to design the printing of wet objects that will form different final 3D structures.

Soft robotics is a growing field of research, focusing on constructing motor-less robots from highly compliant materials, some are similar to those found in living organisms. Soft robotics has a high potential for applications in various fields such as soft grippers, actuators, and biomedical devices. 3D printing of soft robotics presents a novel and promising approach to form objects with complex structures, directly from a digital design. Here, recent developments in the field of materials for 3D printing of soft robotics are summarized, including high-performance flexible and stretchable materials, hydrogels, self-healing materials, and shape memory polymers, as well as fabrication of all-printed robots (multi-material printing, embedded electronics, untethered and autonomous robotics). The current challenges in the fabrication of 3D printed soft robotics, including the materials available and printing abilities, are presented and the recent activities addressing these challenges are also surveyed.