Reconfigurable 4D printing via mechanically robust covalent adaptable network shape memory polymer.

4D printing enables 3D printed structures to change shape over "time" in response to environmental stimulus. Because of relatively high modulus, shape memory polymers (SMPs) have been widely used for 4D printing. However, most SMPs for 4D printing are thermosets, which only have one permanent shape. Despite the efforts that implement covalent adaptable networks (CANs) into SMPs to achieve shape reconfigurability, weak thermomechanical properties of the current CAN-SMPs exclude them from practical applications. Here, we report reconfigurable 4D printing via mechanically robust CAN-SMPs (MRC-SMPs), which have high deformability at both programming and reconfiguration temperatures (>1400%), high Tg (75°C), and high room temperature modulus (1.06 GPa). The high printability for DLP high-resolution 3D printing allows MRC-SMPs to create highly complex SMP 3D structures that can be reconfigured multiple times under large deformation. The demonstrations show that the reconfigurable 4D printing allows one printed SMP structure to fulfill multiple tasks.

Electrothermally controlled origami fabricated by 4D printing of continuous fiber-reinforced composites.

Active origami capable of precise deployment control, enabling on-demand modulation of its properties, is highly desirable in multi-scenario and multi-task applications. While 4D printing with shape memory composites holds great promise to realize such active origami, it still faces challenges such as low load-bearing capacity and limited transformable states. Here, we report a fabrication-design-actuation method of precisely controlled electrothermal origami with excellent mechanical performance and spatiotemporal controllability, utilizing 4D printing of continuous fiber-reinforced composites. The incorporation of continuous carbon fibers empowers electrothermal origami with a controllable actuation process via Joule heating, increased actuation force through improved heat conduction, and enhanced mechanical properties as a result of reinforcement. By modeling the multi-physical and highly nonlinear deploying process, we attain precise control over the active origami, allowing it to be reconfigured and locked into any desired configuration by manipulating activation parameters. Furthermore, we showcase the versatility of electrothermal origami by constructing reconfigurable robots, customizable architected materials, and programmable wings, which broadens the practical engineering applications of origami.

Direct 4D printing of ceramics driven by hydrogel dehydration.

4D printing technology combines 3D printing and stimulus-responsive materials, enabling construction of complex 3D objects efficiently. However, unlike smart soft materials, 4D printing of ceramics is a great challenge due to the extremely weak deformability of ceramics. Here, we report a feasible and efficient manufacturing and design approach to realize direct 4D printing of ceramics. Photocurable ceramic elastomer slurry and hydrogel precursor are developed for the fabrication of hydrogel-ceramic laminates via multimaterial digital light processing 3D printing. Flat patterned laminates evolve into complex 3D structures driven by hydrogel dehydration, and then turn into pure ceramics after sintering. Considering the dehydration-induced deformation and sintering-induced shape retraction, we develop a theoretical model to calculate the curvatures of bent laminate and sintered ceramic part. Then, we build a design flow for direct 4D printing of various complex ceramic objects. This approach opens a new avenue for the development of ceramic 4D printing technology.

Effect of Eccentricity Difference on the Mechanical Response of Microfluidics-Derived Hollow Silica Microspheres during Nanoindentation.

Hollow microspheres as the filler material of syntactic foams have been adopted in extensive practical applications, where the physical parameters and their homogeneity have been proven to be critical factors during the design process, especially for high-specification scenarios. Based on double-emulsion droplet templates, hollow microspheres derived from microfluidics-enabled soft manufacturing have been validated to possess well-controlled morphology and composition with a much narrower size distribution and fewer defects compared to traditional production methods. However, for more stringent requirements, the innate density difference between the core-shell solution of the double-emulsion droplet template shall result in the wall thickness heterogeneity of the hollow microsphere, which will lead to unfavorable mechanical performance deviations. To clarify the specific mechanical response of microfluidics-derived hollow silica microspheres with varying eccentricities, a hybrid method combining experimental nanoindentation and a finite element method (FEM) simulation was proposed. The difference in eccentricity can determine the specific mechanical response of hollow microspheres during nanoindentation, including crack initiation and the evolution process, detailed fracture modes, load-bearing capacity, and energy dissipation capability, which should shed light on the necessity of optimizing the concentricity of double-emulsion droplets to improve the wall thickness homogeneity of hollow microspheres for better mechanical performance.

Hierarchical Bamboo/Silver Nanoparticle Composites for Sustainable Water Purification.

Water reclamation is the most effective way to continuously provide clean water to combat catastrophic global water scarcity. However, current technology for water purification is not conducive to sustainability due to the high energy consumption and negative environmental impact. Here, we introduce an innovative method by utilizing the hierarchical microstructure of bamboo for water purification. Natural bamboo was delignified followed by freeze-drying to obtain a bamboo aerogel with a porosity of 72.0%; then, the bamboo aerogel was coated with silver nanoparticles to form a hierarchical bamboo/silver nanoparticle composite. The scanning electron microscopy images and energy-dispersive X-ray spectroscopy results indicated that the silver nanoparticles were uniformly attached to the parenchyma cell surface. By physical adsorption and catalytic reduction, the bamboo/silver nanoparticle composite was able to degrade methylene blue by more than 96.7%, which is mainly attributed to the large specific surface area of the bamboo providing more space for the purification reaction. This composite can be potentially used for board applications with its high porosity, mechanical reliability, and sustainability.

A volatile microemulsion method of preparing water-soluble photo-absorbers for 3D printing of high-resolution, high-water-content hydrogel structures.

Digital light processing (DLP)-based three-dimensional (3D) printing is an ideal tool to manufacture hydrogel structures in complex 3D forms. Using DLP to print hydrogel structures with high resolution requires the addition of water-soluble photo-absorbers to absorb excess light and confine photopolymerization to the desired area. However, the current photo-absorbers for hydrogel printing are neither efficient to absorb the excess light nor water-soluble. Herein, we report a volatile microemulsion template method that converts a wide range of commercial non-water-soluble photo-absorbers including Sudan orange G, quercetin, and many others to water-soluble nanoparticles with solubility above 1.0 g mL-1. After using these water-soluble photo-absorber nanoparticles, the highest lateral and vertical resolutions of printing high-water-content (70-80 wt%) hydrogels can be improved to 5 µm and 20 µm, respectively. Moreover, the quercetin nanoparticle can be easily washed out so that we achieve colorless and transparent printed hydrogel structures with excellent mechanical deformability and biocompatibility as well as thermally controllable variations on transparency and actuation. The proposed methods pave a new efficient way to develop water-soluble photo-absorbers, which helps to greatly improve the printing resolution of the high-water-content hydrogel structure and would be beneficial to extend the application scope of hydrogels.

Multimaterial 3D printed self-locking thick-panel origami metamaterials.

Thick-panel origami has shown great potential in engineering applications. However, the thick-panel origami created by current design methods cannot be readily adopted to structural applications due to the inefficient manufacturing methods. Here, we report a design and manufacturing strategy for creating thick-panel origami structures with excellent foldability and capability of withstanding cyclic loading. We directly print thick-panel origami through a single fused deposition modeling (FDM) multimaterial 3D printer following a wrapping-based fabrication strategy where the rigid panels are wrapped and connected by highly stretchable soft parts. Through stacking two thick-panel origami panels into a predetermined configuration, we develop a 3D self-locking thick-panel origami structure that deforms by following a push-to-pull mode enabling the origami structure to support a load over 11000 times of its own weight and sustain more than 100 cycles of 40% compressive strain. After optimizing geometric parameters through a self-built theoretical model, we demonstrate that the mechanical response of the self-locking thick-panel origami structure is highly programmable, and such multi-layer origami structure can have a substantially improved impact energy absorption for various structural applications.

Multimaterial Three-Dimensional Printing of Ultraviolet-Curable Ionic Conductive Elastomers with Diverse Polymers for Multifunctional Flexible Electronics.

Ionic conductive elastomers (ICEs) are emerging stretchable and ionic conductive materials that are solvent-free and thus demonstrate excellent thermal stability. Three-dimensional (3D) printing that creates complex 3D structures in free forms is considered as an ideal approach to manufacture sophisticated ICE-based devices. However, the current technologies constrain 3D printed ICE structures in a single material, which greatly limits functionality and performance of ICE-based devices and machines. Here, we report a digital light processing (DLP)-based multimaterial 3D printing capability to seemly integrate ultraviolet-curable ICE (UV-ICE) with nonconductive materials to create ionic flexible electronic devices in 3D forms with enhanced performance. This unique capability allows us to readily manufacture various 3D flexible electronic devices. To demonstrate this, we printed UV-ICE circuits into polymer substrates with different mechanical properties to create resistive strain and force sensors; we printed flexible capacitive sensors with high sensitivity (2 kPa-1) and a wide range of measured pressures (from 5 Pa to 550 kPa) by creating a complex microstructure in the dielectric layer; we even realized ionic conductor-activated four-dimensional (4D) printing by printing a UV-ICE circuit into a shape memory polymer substrate. The proposed approach paves a new efficient way to realize multifunctional flexible devices and machines by bonding ICEs with other polymers in 3D forms.

Centrifugal multimaterial 3D printing of multifunctional heterogeneous objects.

There are growing demands for multimaterial three-dimensional (3D) printing to manufacture 3D object where voxels with different properties and functions are precisely arranged. Digital light processing (DLP) is a high-resolution fast-speed 3D printing technology suitable for various materials. However, multimaterial 3D printing is challenging for DLP as the current multimaterial switching methods require direct contact onto the printed part to remove residual resin. Here we report a DLP-based centrifugal multimaterial (CM) 3D printing method to generate large-volume heterogeneous 3D objects where composition, property and function are programmable at voxel scale. Centrifugal force enables non-contact, high-efficiency multimaterial switching, so that the CM 3D printer can print heterogenous 3D structures in large area (up to 180 mm × 130 mm) made of materials ranging from hydrogels to functional polymers, and even ceramics. Our CM 3D printing method exhibits excellent capability of fabricating digital materials, soft robots, and ceramic devices.

Latent Pathogenic Fungi in the Medicinal Plant Houttuynia cordata Thunb. Are Modulated by Secondary Metabolites and Colonizing Microbiota Originating from Soil.

Latent pathogenic fungi (LPFs) affect plant growth, but some of them may stably colonize plants. LPFs were isolated from healthy Houttuynia cordata rhizomes to reveal this mechanism and identified as Ilyonectria liriodendri, an unidentified fungal sp., and Penicillium citrinum. Sterile H. cordata seedlings were cultivated in sterile or non-sterile soils and inoculated with the LPFs, followed by the plants' analysis. The in vitro antifungal activity of H. cordata rhizome crude extracts on LPF were determined. The effect of inoculation of sterile seedlings by LPFs on the concentrations of rhizome phenolics was evaluated. The rates of in vitro growth inhibition amongst LPFs were determined. The LPFs had a strong negative effect on H. cordata in sterile soil; microbiota in non-sterile soil eliminated such influence. There was an interactive inhibition among LPFs; the secondary metabolites also regulated their colonization in H. cordata rhizomes. LPFs changed the accumulation of phenolics in H. cordata. The results provide that colonization of LPFs in rhizomes was regulated by the colonizing microbiota of H. cordata, the secondary metabolites in the H. cordata rhizomes, and the mutual inhibition and competition between the different latent pathogens.

CuCo2O4 Hollow Microspheres with Graphene Composite Targeting Superior Lithium-Ion Storage.

CuCo2O4, a type of promising lithium-ion storage material, exhibits high electrochemical properties in lithium-ion batteries and enormous economic benefits. However, its practical application is limited by problems such as structural collapse and electrochemical stability during the charging and discharging process. In this work, the reduced graphene oxide (rGO)-coated CuCo2O4 (CuCo2O4/rGO) hollow microspheres were successfully prepared by electrostatic self-assembly. The CuCo2O4/rGO electrode shows an outstanding capability for lithium-ion storage and a remarkable rate capacity, e.g., 445 mA h g-1 at 5 A g-1. After 150 cycles at 0.1 A g-1, the reversible capacity of the CuCo2O4/rGO electrode is as high as 1080 mA h g-1, and it can still retain about 530 mA h g-1 in the 400th cycle at 1 A g-1. The hollow microspheres with mesoporous shells can cause electrolyte penetration into the spherical shell to effectively shorten the transfer distance of lithium ions, and the encapsulation of graphene improves the conductivity and stability of CuCo2O4, which endows CuCo2O4/rGO with a wonderful Li+ storage performance. It is proved that this is an efficient method to improve the electrochemical performance of metal compounds for better applications in energy storage.

Endophytic fungi stimulate the concentration of medicinal secondary metabolites in houttuynia cordata thunb.

Endophytic fungi usually establish a symbiotic relationship with the host plant and affect its growth. In order to evaluate the impact of endophytic fungi on the Chinese herbal medicinal plant Houttuynia cordata Thunb., three endophytes isolated from the rhizomes of H. cordata, namely Ilyonectria liriodendra (IL), unidentified fungal sp. (UF), and Penicillium citrinum (PC), were co-cultured individually with H. cordata in sterile soil for 60 days. Analysis of the results showed that the endophytes stimulated the host plant in different ways: IL increased the growth of rhizomes and the accumulation of most of the phenolics and volatiles, UF promoted the accumulation of the medicinal compounds afzelin, decanal, 2-undecanone, and borneol without influencing host plant growth, and PC increased the fresh weight, total leaf area and height of the plants, as well as the growth of the rhizomes, but had only a small effect on the concentration of major secondary metabolites. Our results proved that the endophytic fungi had potential practical value in terms of the production of Chinese herbal medicines, having the ability to improve the yield and accumulation of medicinal metabolites.

Mechanically Robust and UV-Curable Shape-Memory Polymers for Digital Light Processing Based 4D Printing.

4D printing is an emerging fabrication technology that enables 3D printed structures to change configuration over "time" in response to an environmental stimulus. Compared with other soft active materials used for 4D printing, shape-memory polymers (SMPs) have higher stiffness, and are compatible with various 3D printing technologies. Among them, ultraviolet (UV)-curable SMPs are compatible with Digital Light Processing (DLP)-based 3D printing to fabricate SMP-based structures with complex geometry and high-resolution. However, UV-curable SMPs have limitations in terms of mechanical performance, which significantly constrains their application ranges. Here, a mechanically robust and UV-curable SMP system is reported, which is highly deformable, fatigue resistant, and compatible with DLP-based 3D printing, to fabricate high-resolution (up to 2 µm), highly complex 3D structures that exhibit large shape change (up to 1240%) upon heating. More importantly, the developed SMP system exhibits excellent fatigue resistance and can be repeatedly loaded more than 10 000 times. The development of the mechanically robust and UV-curable SMPs significantly improves the mechanical performance of the SMP-based 4D printing structures, which allows them to be applied to engineering applications such as aerospace, smart furniture, and soft robots.

Color-Changeable Four-Dimensional Printing Enabled with Ultraviolet-Curable and Thermochromic Shape Memory Polymers.

Four-dimensional (4D) printing, which enables 3D printed structures to alter shapes over time, is attracting increasing attention because of its exciting potential in various applications. Among all the 4D printing materials, shape memory polymers (SMPs) have a higher stiffness and faster response rate and therefore are considered as one of the most promising 4D printing materials. However, the current studies of SMP-based 4D printing mainly focused on the deformation behavior and structural design of 4D printed structures. An additional function such as color change is desired for 4D printed structure, which would be potentially beneficial to the applications such as anti-counterfeiting, encryption, and bioinspired camouflage. In this paper, we report an ultraviolet (UV)-curable and thermochromic (UVT) SMP system that enables color-changeable 4D printing. The UVT SMP system is acrylate-based, thus highly UV-curable and compatible with PµSL-based high-resolution 3D printing technique. Thermochromism is imparted by adding the thermochromic microcapsules to the UVT SMP system, which allows the printed structures to reversibly change colors upon heating and cooling. To demonstrate its extraordinary thermochromic and mechanical performance, we use UVT SMP to print QR codes and multilevel anti-counterfeiting patterns which can hide the visible information at room temperature and visualize the information by encrypting, decrypting, and encrypting again steps with the shape-color recovery process. The development of UVT SMP will significantly advance current applications of SMP-based 4D printing, especially for anti-counterfeiting and safe data recording.

Free-Standing Hybrid Graphene Paper Encapsulating Nanostructures for High Cycle-Life Supercapacitors.

The incorporation of spacers between graphene sheets has been investigated as an effective method to improve the electrochemical performance of graphene papers (GPs) for supercapacitors. Here, we report the design of free-standing GP@NiO and GP@Ni hybrid GPs in which NiO nanoclusters and Ni nanoparticles are encapsulated into graphene sheets through electrostatic assembly and subsequent vacuum filtration. The encapsulated NiO nanoclusters and Ni nanoparticles can mitigate the restacking of graphene sheets, providing sufficient spaces for high-speed ion diffusion and electron transport. In addition, the spacers strongly bind to graphene sheets, which can efficiently improve the electrochemical stability. Therefore, at a current density of 0.5 A g-1 , the GP@NiO and GP@Ni electrodes exhibit higher specific capacitances of 306.9 and 246.1 F g-1 than the GP electrode (185.7 F g-1 ). The GP@NiO and GP@Ni electrodes exhibit capacitance retention of 98.7 % and 95.6 % after 10000 cycles, demonstrating an outstanding cycling stability. Additionally, the GP@NiO∥GP@Ni delivers excellent cycling stability (93.7 % after 10 000 cycles) and high energy density. These free-standing encapsulated hybrid GPs have great potential as electrode for high-performance supercapacitors.

Three-Dimensional Hierarchical Structure ZnO@C@NiO on Carbon Cloth for Asymmetric Supercapacitor with Enhanced Cycle Stability.

In this work, we synthesized the hierarchical ZnO@C@NiO core-shell nanorods arrays (CSNAs) grown on a carbon cloth (CC) conductive substrate by a three-step method involving hydrothermal and chemical bath methods. The morphology and chemical structure of the hybrid nanoarrays were characterized in detail. The combination and formation mechanism was proposed. The conducting carbon layer between ZnO and NiO layers can efficiently enhance the electric conductivity of the integrated electrodes, and also protect the corrosion of ZnO in an alkaline solution. Compared with ZnO@NiO nanorods arrays (NAs), the NiO in CC/ZnO@C@NiO electrodes, which possess a unique multilevel core-shell nanostructure exhibits a higher specific capacity (677 C/g at 1.43 A/g) and an enhanced cycling stability (capacity remain 71% after 5000 cycles), on account of the protection of carbon layer derived from glucose. Additionally, a flexible all-solid-state supercapacitor is readily constructed by coating the PVA/KOH gel electrolyte between the ZnO@C@NiO CSNAs and commercial graphene. The energy density of this all-solid-state device decreases from 35.7 to 16.0 Wh/kg as the power density increases from 380.9 to 2704.2 W/kg with an excellent cycling stability (87.5% of the initial capacitance after 10000 cycles). Thereby, the CC/ ZnO@C@NiO CSNAs of three-dimensional hierarchical structure is promising electrode materials for flexible all-solid-state supercapacitors.

Titanium Dioxide Engineered for Near-dispersionless High Terahertz Permittivity and Ultra-low-loss.

Realising engineering ceramics to serve as substrate materials in high-performance terahertz(THz) that are low-cost, have low dielectric loss and near-dispersionless broadband, high permittivity, is exceedingly demanding. Such substrates are deployed in, for example, integrated circuits for synthesizing and converting nonplanar and 3D structures into planar forms. The Rutile form of titanium dioxide (TiO2) has been widely accepted as commercially economical candidate substrate that meets demands for both low-loss and high permittivities at sub-THz bands. However, the relationship between its mechanisms of dielectric response to the microstructure have never been systematically investigated in order to engineer ultra-low dielectric-loss and high value, dispersionless permittivities. Here we show TiO2 THz dielectrics with high permittivity (ca. 102.30) and ultra-low loss (ca. 0.0042). These were prepared by insight gleaned from a broad use of materials characterisation methods to successfully engineer porosities, second phase, crystallography shear-planes and oxygen vacancies during sintering. The dielectric loss achieved here is not only with negligible dispersion over 0.2-0.8 THz, but also has the lowest value measured for known high-permittivity dielectrics. We expect the insight afforded by this study will underpin the development of subwavelength-scale, planar integrated circuits, compact high Q-resonators and broadband, slow-light devices in the THz band.

Luminescence of delafossite-type CuAlO2 fibers with Eu substitution for Al cations.

CuAlO2 has been examined as a potential luminescent material by substituting Eu for Al cations in the delafossite structure. CuAlO2:Eu3+ nanofibers have been prepared via electrospinning for the ease of mitigating synthesis requirements and for future optoelectronics and emerging applications. Single-phase CuAlO2 fibers could be obtained at a temperature of 1100 °C in air. The Eu was successfully doped in the delafossite structure and two strong emission bands at ~405 and 610 nm were observed in the photoluminescence spectra. These bands are due to the intrinsic near-band-edge transition of CuAlO2 and the f-f transition of the Eu3+ activator, respectively. Further electrical characterization indicated that these fibers exhibit semiconducting behavior and the introduction of Eu could act as band-edge modifiers, thus changing the thermal activation energies. In light of this study, CuAlO2:Eu3+ fibers with both strong photoluminescence and p-type conductivity could be produced by tailoring the rare earth doping concentrations.

Three-dimensional Nitrogen-Doped Graphene Supported Molybdenum Disulfide Nanoparticles as an Advanced Catalyst for Hydrogen Evolution Reaction.

An efficient three-dimensional (3D) hybrid material of nitrogen-doped graphene sheets (N-RGO) supporting molybdenum disulfide (MoS(2)) nanoparticles with high-performance electrocatalytic activity for hydrogen evolution reaction (HER) is fabricated by using a facile hydrothermal route. Comprehensive microscopic and spectroscopic characterizations confirm the resulting hybrid material possesses a 3D crumpled few-layered graphene network structure decorated with MoS(2) nanoparticles. Electrochemical characterization analysis reveals that the resulting hybrid material exhibits efficient electrocatalytic activity toward HER under acidic conditions with a low onset potential of 112 mV and a small Tafel slope of 44 mV per decade. The enhanced mechanism of electrocatalytic activity has been investigated in detail by controlling the elemental composition, electrical conductance and surface morphology of the 3D hybrid as well as Density Functional Theory (DFT) calculations. This demonstrates that the abundance of exposed active sulfur edge sites in the MoS(2) and nitrogen active functional moieties in N-RGO are synergistically responsible for the catalytic activity, whilst the distinguished and coherent interface in MoS(2)/N-RGO facilitates the electron transfer during electrocatalysis. Our study gives insights into the physical/chemical mechanism of enhanced HER performance in MoS(2)/N-RGO hybrids and illustrates how to design and construct a 3D hybrid to maximize the catalytic efficiency.