Versatile Patterning of Liquid Metal via Multiphase 3D Printing.

This paper presents a scalable and straightforward technique for the immediate patterning of liquid metal/polymer composites via multiphase 3D printing. Capitalizing on the polymer's capacity to confine liquid metal (LM) into diverse patterns. The interplay between distinctive fluidic properties of liquid metal and its self-passivating oxide layer within an oxidative environment ensures a resilient interface with the polymer matrix. This study introduces an inventive approach for achieving versatile patterns in eutectic gallium indium (EGaIn), a gallium alloy. The efficacy of pattern formation hinges on nozzle's design and internal geometry, which govern multiphase interaction. The interplay between EGaIn and polymer within the nozzle channels, regulated by variables such as traverse speed and material flow pressure, leads to periodic patterns. These patterns, when encapsulated within a dielectric polymer polyvinyl alcohol (PVA), exhibit an augmented inherent capacitance in capacitor assemblies. This discovery not only unveils the potential for cost-effective and highly sensitive capacitive pressure sensors but also underscores prospective applications of these novel patterns in precise motion detection, including heart rate monitoring, and comprehensive analysis of gait profiles. The amalgamation of advanced materials and intricate patterning techniques presents a transformative prospect in the domains of wearable sensing and comprehensive human motion analysis.

Characterization of PEDOT:PSS Nanofilms Printed via Electrically Assisted Direct Ink Deposition with Ultrasonic Vibrations.

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) has emerged as a promising conductive polymer for constructing efficient hole-transport layers (HTLs) in perovskite solar cells (PSCs). However, conventional fabrication methods, such as spin coating, spray coating, and slot-die coating, have resulted in PEDOT:PSS nanofilms with limited performance, characterized by a low density and non-uniform nanostructures. We introduce a novel 3D-printing approach called electrically assisted direct ink deposition with ultrasonic vibrations (EF-DID-UV) to overcome these challenges. This innovative printing method combines programmable acoustic field modulation with electrohydrodynamic spraying, providing a powerful tool for controlling the PEDOT:PSS nanofilm's morphology precisely. The experimental findings indicate that when PEDOT:PSS nanofilms are crafted using horizontal ultrasonic vibrations, they demonstrate a uniform dispersion of PEDOT:PSS nanoparticles, setting them apart from instances involving vertical ultrasonic vibrations, both prior to and after the printing process. In particular, when horizontal ultrasonic vibrations are applied at a low amplitude (0.15 A) during printing, these nanofilms showcase exceptional wettability performance, with a contact angle of 16.24°, and impressive electrical conductivity of 2092 Ω/square. Given its ability to yield high-performance PEDOT:PSS nanofilms with precisely controlled nanostructures, this approach holds great promise for a wide range of nanotechnological applications, including the production of solar cells, wearable sensors, and actuators.

Ultrafast and Large-Scale Fabrication of PEDOT:PSS Nanofilms Using Electrical-Field-Assisted Direct Ink Deposition.

The importance of conductive polymers has significantly increased over the decade due to their various applications, such as in electronic devices, sensors, and photovoltaics. Poly(3,4-ethylene dioxythiophene) polystyrene sulfonate (PEDOT:PSS) is one of the most successfully and widely used polymers in practical applications. Spin coating is extensively used to fabricate these conductive films; however, it has disadvantages. It is inherently a batch process with relatively low output and high solution wastage. To address these issues, we developed a novel printing process called electrical-field-assisted direct ink deposition (EF-DID), which yields a continuous, homogenous film with high electrical conductivity. In this process, we studied the formation of nanodroplets under an electrical field and their effects on film characteristics. Furthermore, dimethyl sulfoxide (DMSO) was considered as an additive solvent to increase the conductivity and wettability of the films. We then compared EF-DID-printed PEDOT:PSS films with spin-coated films to better understand the film properties. Finally, inverted perovskite solar cell devices were fabricated and compared, where the PEDOT:PSS layers were prepared by EF-DID printing and spin coating. Based on the experimental results, a solution of 20% PEDOT:PSS in DMSO (vol/vol) printed by EF-DID for 15 s provided optimal morphology.

Stretchable Nanolayered Thermoelectric Energy Harvester on Complex and Dynamic Surfaces.

Thermoelectric generators (TEGs) provide a unique solution for energy harvesting from waste heat, presenting a potential solution for green energy. However, traditional rigid and flexible TEGs cannot work on complex and dynamic surfaces. Here, we report a stretchable TEG (S-TEG) (over 50% stretchability of the entire device) that is geometrically suitable for various complex and dynamic surfaces of heat sources. The S-TEG consists of hot-pressed nanolayered p-(Sb2Te3) and n-(Bi2Te3)-type thermoelectric couple arrays and exploits the wavy serpentine interconnects to integrate all units. The internal resistance of a 10 × 10 array is 22 ohm, and the output power is ∼0.15 mW/cm2 at ΔT = 19 K on both developable and nondevelopable surfaces, which are much improved compared with those of existing S-TEGs. The energy harvesting of S-TEG from the dynamic surfaces of the human skin offers a potential energy solution for the wearable devices for health monitoring.

A Novel Ultra-Wideband Electromagnetic-Wave-Absorbing Metastructure Inspired by Bionic Gyroid Structures.

Traditional honeycomb-like structural electromagnetic (EM)-wave-absorbing materials have been widely used in various equipment as multifunctional materials. However, current EM-wave-absorbing materials are limited by narrow absorption bandwidths and incidence angles because of their anisotropic structural morphology. The work presented here proposes a novel EM-wave-absorbing metastructure with an isotropic morphology inspired by the gyroid microstructures seen in Parides sesostris butterfly wings. A matching redesign methodology between the material and subwavelength scale properties of the gyroid microstructure is proposed, inspired by the interaction mechanism between the microstructure and the material properties on the EM-wave-absorption performance of the prepared metastructure. The bioinspired metastructure is fabricated by additive manufacturing (AM) and subsequent coating through dipping processes, filled with dielectric lossy materials. Based on simulations and experiments, the metastructure designed in this work exhibits an ultrawide absorption bandwidth covering the frequency range of 2-40 GHz with a fractional bandwidth of 180% at normal incidence. Moreover, the metastructure has a stable frequency response when the incident angle is 60° under transverse electric (TE) and transverse magnetic (TM) polarization. Finally, the synergistic mechanism between the microstructure and the material is elucidated, which provides a new paradigm for the design of novel ultra-broadband EM-absorbing materials.

3D Printing of Nacre-Inspired Structures with Exceptional Mechanical and Flame-Retardant Properties.

Flame-retardant and thermal management structures have attracted great attention due to the requirement of high-temperature exposure in industrial, aerospace, and thermal power fields, but the development of protective fire-retardant structures with complex shapes to fit arbitrary surfaces is still challenging. Herein, we reported a rotation-blade casting-assisted 3D printing process to fabricate nacre-inspired structures with exceptional mechanical and flame-retardant properties, and the related fundamental mechanisms are studied. 3-(Trimethoxysilyl)propyl methacrylate (TMSPMA) modified boron nitride nanoplatelets (BNs) were aligned by rotation-blade casting during the 3D printing process to build the "brick and mortar" architecture. The 3D printed structures are more lightweight, while having higher fracture toughness than the natural nacre, which is attributed to the crack deflection, aligned BN (a-BNs) bridging, and pull-outs reinforced structures by the covalent bonding between TMSPMA grafted a-BNs and polymer matrix. Thermal conductivity is enhanced by 25.5 times compared with pure polymer and 5.8 times of anisotropy due to the interconnection of a-BNs. 3D printed heat-exchange structures with vertically aligned BNs in complex shapes were demonstrated for efficient thermal control of high-power light-emitting diodes. 3D printed helmet and armor with a-BNs show exceptional mechanical and fire-retardant properties, demonstrating integrated mechanical and thermal protection.

Mesenchymal stem cells and three-dimensional-osteoconductive scaffold regenerate calvarial bone in critical size defects in swine.

Craniofacial bones protect vital organs, perform important physiological functions, and shape facial identity. Critical-size defects (CSDs) in calvarial bones, which will not heal spontaneously, are caused by trauma, congenital defects, or tumor resections. They pose a great challenge for patients and physicians, and significantly compromise quality of life. Currently, calvarial CSDs are treated either by allogenic or autologous grafts, metal or other synthetic plates that are associated with considerable complications. While previous studies have explored tissue regeneration for calvarial defects, most have been done in small animal models with limited translational value. Here we define a swine calvarial CSD model and show a novel approach to regenerate high-quality bone in these defects by combining mesenchymal stem cells (MSCs) with a three-dimensional (3D)-printed osteoconductive HA/TCP scaffold. Specifically, we have compared the performance of dental pulp neural crest MSCs (DPNCCs) to bone marrow aspirate (BMA) combined with a 3D-printed HA/TCP scaffold to regenerate bone in a calvarial CSD (>7.0 cm2 ). Both DPNCCs and BMA loaded onto the 3D-printed osteoconductive scaffold support the regeneration of calvarial bone with density, compression strength, and trabecular structures similar to native bone. Our study demonstrates a novel application of an original scaffold design combined with DPNCCs or BMA to support regeneration of high-quality bone in a newly defined and clinically relevant swine calvarial CSD model. This discovery may have important impact on bone regeneration beyond the craniofacial region and will ultimately benefit patients who suffer from debilitating CSDs.

Electrically assisted 3D printing of nacre-inspired structures with self-sensing capability.

Lightweight and strong structural materials attract much attention due to their strategic applications in sports, transportation, aerospace, and biomedical industries. Nacre exhibits high strength and toughness from the brick-and-mortar-like structure. Here, we present a route to build nacre-inspired hierarchical structures with complex three-dimensional (3D) shapes by electrically assisted 3D printing. Graphene nanoplatelets (GNs) are aligned by the electric field (433 V/cm) during 3D printing and act as bricks with the polymer matrix in between as mortar. The 3D-printed nacre with aligned GNs (2 weight %) shows lightweight property (1.06 g/cm3) while exhibiting comparable specific toughness and strength to the natural nacre. In addition, the 3D-printed lightweight smart armor with aligned GNs can sense its damage with a hesitated resistance change. This study highlights interesting possibilities for bioinspired structures, with integrated mechanical reinforcement and electrical self-sensing capabilities for biomedical applications, aerospace engineering, as well as military and sports armors.

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.

Recent Progress in Biomimetic Additive Manufacturing Technology: From Materials to Functional Structures.

Nature has developed high-performance materials and structures over millions of years of evolution and provides valuable sources of inspiration for the design of next-generation structural materials, given the variety of excellent mechanical, hydrodynamic, optical, and electrical properties. Biomimicry, by learning from nature's concepts and design principles, is driving a paradigm shift in modern materials science and technology. However, the complicated structural architectures in nature far exceed the capability of traditional design and fabrication technologies, which hinders the progress of biomimetic study and its usage in engineering systems. Additive manufacturing (three-dimensional (3D) printing) has created new opportunities for manipulating and mimicking the intrinsically multiscale, multimaterial, and multifunctional structures in nature. Here, an overview of recent developments in 3D printing of biomimetic reinforced mechanics, shape changing, and hydrodynamic structures, as well as optical and electrical devices is provided. The inspirations are from various creatures such as nacre, lobster claw, pine cone, flowers, octopus, butterfly wing, fly eye, etc., and various 3D-printing technologies are discussed. Future opportunities for the development of biomimetic 3D-printing technology to fabricate next-generation functional materials and structures in mechanical, electrical, optical, and biomedical engineering are also outlined.