Self‐Healing and Stretchable 3D‐Printed Organic Thermoelectrics

With the advent of flexible and wearable electronics and sensors, there is an urgent need to develop energy‐harvesting solutions that are compatible with such wearables. However, many of the proposed energy‐harvesting solutions lack the necessary mechanical properties, which make them susceptible to damage by repetitive and continuous mechanical stresses, leading to serious degradation in device performance. Developing new energy materials that possess high deformability and self‐healability is essential to realize self‐powered devices. Herein, a thermoelectric ternary composite is demonstrated that possesses both self‐healing and stretchable properties produced via 3D‐printing method. The ternary composite films provide stable thermoelectric performance during viscoelastic deformation, up to 35% tensile strain. Importantly, after being completely severed by cutting, the composite films autonomously recover their thermoelectric properties with a rapid response time of around one second. Using this self‐healable and solution‐processable composite, 3D‐printed thermoelectric generators are fabricated, which retain above 85% of their initial power output, even after repetitive cutting and self‐healing. This approach represents a significant step in achieving damage‐free and truly wearable 3D‐printed organic thermoelectrics.     

Diels–Alder Reversible Thermoset 3D Printing: Isotropic Thermoset Polymers via Fused Filament Fabrication

This study presents a new 3D printing process, the Diels–Alder reversible thermoset (DART) process, and a first generation of printable DART resins, which exhibit thermoset properties at use temperatures, ultralow melt viscosity at print temperatures, smooth part surface finish, and as‐printed isotropic mechanical properties. This study utilizes dynamic covalent chemistry based on reversible furan‐maleimide Diels–Alder linkages in the polymers, which can be decrosslinked and melt‐processed during printing between 90 and 150 °C, and recrosslinked at lower temperatures to their entropically favored state. This study compares the first generation of DART materials to commonly 3D printed high‐toughness thermoplastics. Parts printed from typical fused filament fabrication compatible materials exhibit anisotropy of more than 50% and sometimes upward of 98% in toughness when deformed along the build direction, while the first generation of DART materials exhibit less than 4% toughness reduction when deformed along the build direction. At room temperature, the toughest DART materials exhibit baseline toughness of 18.59 ± 0.91 and 18.36 ± 0.57 MJ m^?3 perpendicular and parallel to the build direction, respectively. DART printing will enable chemists, polymer engineers, materials scientists, and industrial designers to translate new robust materials possessing targeted thermomechanical properties, multiaxial toughness, smooth surface finish, and low anisotropy.     

Table Salt as a Template to Prepare Reusable Porous PVDF–MWCNT Foam for Separation of Immiscible Oils/Organic Solvents and Corrosive Aqueous Solutions

Many advanced materials are designed for separation of immiscible oils/organic solvents and aqueous solutions, including poly(vinylidene fluoride) (PVDF)‐based materials with superwettability. However, due to the limited solubility of PVDF, techniques (e.g., phase inversion and electrospinning) often involve the use of toxic organic solvents. Here a facile organic solvent‐free method is described to prepare a porous PVDF–MWCNT (multiwalled carbon nanotube) foam using table salt as a sacrificial template. The porous PVDF–MWCNT foam is characterized as superhydrophobic–superoleophilic with good elasticity due to its 3D porosity and low surface energy. The foam exhibits high adsorption capacity to a variety of oils/organic solvents and can be easily reused by squeezing, heating, or releasing in other solvents. Moreover, the foam is highly resistant toward UV exposure, corrosive aqueous solutions such as acidic, alkaline, salty solutions, and turbulent environments, and shows effective oils/organic solvents removal in these complex environments. The continuous separation of immiscible oils/organic solvents and corrosive aqueous solutions with vacuum assistance is also presented. The organic solvent‐free and reusable PVDF–MWCNT foam is a promising candidate for large‐scale industrial separation of oils/organic solvents and water in corrosive and turbulent conditions.     

Direct Ink Writing of Polymer Composite Electrolytes with Enhanced Thermal Conductivities

Proper distribution of thermally conductive nanomaterials in polymer batteries offers new opportunities to mitigate performance degradations associated with local hot spots and safety concerns in batteries. Herein, a direct ink writing (DIW) method is utilized to fabricate polyethylene oxide (PEO) composite polymers electrolytes (CPE) embedded with silane-treated hexagonal boron nitride (S-hBN) platelets and free of any volatile organic solvents. It is observed that the S-hBN platelets are well aligned in the printed CPE during the DIW process. The in-plane thermal conductivity of the printed CPE with the aligned S-hBN platelets is 1.031 W ⁻¹ K⁻¹, which is about 1.7 times that of the pristine CPE with the randomly dispersed S-hBN platelets (0.612 W ⁻¹ K⁻¹). Thermal imaging shows that the peak temperature (°C) of the printed electrolytes is 24.2% lower than that of the CPE without S-hBN, and 10.6% lower than that of the CPE with the randomly dispersed S-hBN, indicating a superior thermal transport property. Lithium-ion half-cells made with the printed CPE and LiFePO₄ cathode displayed high specific discharge capacity of 146.0 mAh g⁻¹ and stable Coulombic efficiency of 91% for 100 cycles at room temperature. This work facilitates the development of printable thermally-conductive polymers for safer battery operations.     

Bio‐Inspired,Water‐Soluble to Insoluble Self‐Conversion for Flexible,Biocompatible, Transparent,Catecholamine Polysaccharide Thin Films

In nature, a variety of functional water‐insoluble organic materials are biologically synthesized in aqueous conditions without chemical additives and organic solvents. Insect cuticle, crustacean shells, and many others are representative examples. The insoluble materials are prepared by enzyme reactions and programmed self‐assembly in water from water‐soluble precursors. If the water‐basis could be adapted, environment‐friendly strategy developed in nature, many problems caused by the vast consumption of petroleum‐based olefin materials could be solved or significantly attenuated. Here, the spontaneous formation of water‐insoluble, biocompatible films from a water‐soluble polymer is demonstrated without using any chemical additives and organic solvents. It is found that a water‐soluble chitosan–catechol polymeric precursor is spontaneously self‐converted to flexible water‐insoluble thin film by simple dehydration. The preparation of mechanically robust, water‐insoluble, flexible, transparent chitosan–catechol film is a completely unexpected result because most water‐soluble polymers exist as powders when dehydrated. The film can be used as a bag similar to polyvinyl one and is multifunctional and biocompatible for drug delivery depots and tissue engineering applications.     

Printed Capacitive Sensors Based on Ionic Liquid/Metal-Organic Framework Composites for Volatile Organic Compounds Detection

In this paper, the potential of 2D printing technologies to create thin film gas sensors from ionic liquid (IL)/metal–organic framework (MOF) composites is evaluated. To accomplish this, the MOF is synthesized solvothermally, and impregnated with the IL. The structure and basic properties of the IL/MOF composites are characterized using thermal, spectroscopic, and X-ray diffraction techniques, and the resultant sensing capacity of the bulk material is evaluated by impedance spectroscopy. The IL/MOF systems are then integrated into a 2D printed silver capacitive circuit by spray and tested on a custom-made gas flow apparatus. Exposure of the IL/MOF based sensors to water, acetone, and ethanol induces a repetitive variation of the capacitance (from 0.05 to 7 pF) that is dependent on the nature of the gas. IL/MOF based sensors can detect changes in concentrations in the range of 10k–100k ppm in less than a second. The conclusions of this work are the first steps towards the development of 2D printed sensors based on IL/MOF materials. Such materials offer countless possibilities to tailor the porosity, chemistry, selectivity, and electrical response to make the sensor suitable to detect the desired analyte.     

Water‐Stable Silk Films with Reduced β‐Sheet Content

Silk fibers have outstanding mechanical properties. These fibers are insoluble in organic solvents and water, are biocompatible, and exhibit slow biodegradation in vitro and in vivo due to the hydrophobic nature of the protein and the presence of a high content of β‐sheet structure. Regenerated silk fibroin can be processed into a variety of materials normally stabilized by the induction of β‐sheet formation through the use of solvents or by physical stretching. To extend the biomaterial utility of silk proteins, options to form water‐stable silk‐based materials with reduced β‐sheet formation would be desirable. To address this need for more rapidly degradable silk biomaterials, we report the preparation of water‐stable films from regenerated silk fibroin solutions, with reduced β‐sheet content. The keys to this process are the preparation of concentrated (8 % by weight) aqueous solutions of fibroin and a subsequent water‐based annealing procedure. These new materials degrade more rapidly due to the reduced β‐sheet content, as determined in vitro via enzymatic hydrolysis, yet support human adult stem‐cell expansion in vitro in a similar or improved fashion to the crystallized proteins in film form. These new silk‐based materials extend the range of biomaterial properties that can be generated from this unique family of proteins.     

Hydrophilic Nanotube Supported Graphene–Water Dispersible Carbon Superstructure with Excellent Conductivity

In this work, it is shown that the hydrophilic functionalized multiwall carbon nanotubes (MWCNs) can stabilize a large amount of pristine graphene nanosheets in pure water without the assistance of surfactants, ionic liquids, or hydrophilic polymers. Role of stabilizer is conveyed by highly hydrophilic carbon nanotubes, functionalized by dihydroxy phenyl groups, affording a stable dispersion at concentrations as high as 15 mg mL^?1. Such multidimensional (2D/1D) graphene/MWCN hybrid is found to be dispersible also in other polar organic solvents such as ethanol, isopropanol, N,N‐dimethylformamide, ethylene glycol, and their mixtures. High‐resolution transmission microscopy and atomic force microscopy (AFM) including a liquid mode AFM manifest several types of interaction including trapping of multiwalled carbon nanotubes between the graphene sheets or the modification of graphene edges. Molecular dynamic simulations show that formation of an assembly is kinetically controlled. Importantly, the hybrid can be deposited on the paper by drop casting or dispersed in water‐soluble polymers resulting in record values of electrical conductivity (sheet resistance up to R_s ≈ 25 Ω sq^?1 for free hybrid material and R_s ≈ 1300 Ω sq^?1 for a polyvinilalcohol/hybrid composite film). Thus, these novel water dispersible carbon superstructures reveal a high application potential as conductive inks for inkjet printing or as highly conductive polymers.     

Metallic Architectures from 3D‐Printed Powder‐Based Liquid Inks

A new method for complex metallic architecture fabrication is presented, through synthesis and 3D‐printing of a new class of 3D‐inks into green‐body structures followed by thermochemical transformation into sintered metallic counterparts. Small and large volumes of metal‐oxide, metal, and metal compound 3D‐printable inks are synthesized through simple mixing of solvent, powder, and the biomedical elastomer, polylactic‐co‐glycolic acid (PLGA). These inks can be 3D‐printed under ambient conditions via simple extrusion at speeds upwards of 150 mm s^–1 into millimeter‐ and centimeter‐scale thin, thick, high aspect ratio, hollow and enclosed, and multi‐material architectures. The resulting 3D‐printed green‐bodies can be handled immediately, are remarkably robust, and may be further manipulated prior to metallic transformation. Green‐bodies are transformed into metallic counterparts without warping or cracking through reduction and sintering in a H₂ atmosphere at elevated temperatures. It is shown that primary metal and binary alloy structures can be created from inks comprised of single and mixed oxide powders, and the versatility of the process is illustrated through its extension to more than two dozen additional metal‐based materials. A potential application of this new system is briefly demonstrated through cyclic reduction and oxidation of 3D‐printed iron oxide constructs, which remain intact through numerous redox cycles.     

Tailored and Highly Stretchable Sensor Prepared by Crosslinking an Enhanced 3D Printed UV-Curable Sacrificial Mold

Taking advantage of unlimited geometry design, 3D printed sacrificial mold cast with highly conductive polymer composites is used to prepare a sensor with designed structures. However, the disposal of the mold in a mild condition while the refined structures can be maintained is still a challenge. Herein, a bifunctional monomer hydrolyzable hindered urea acrylate is synthesized to create a cross-linked polymer network, preventing the dissolution of printed parts in the uncured resin. 3D printed scaffolds can be hydrolyzed in hot water, which provides an attractive option for sacrificial molds. Also, a porous flexible strain sensor (PFSS) is fabricated by casting polyurethane/carbon nanotubes composites into the sacrificial molds, which demonstrates a high stretchability (≈510%) and an excellent recoverability. Meantime, the pressure sensitivity (0.111 kPa⁻¹) and a long-term electrical resistance of PFSS is characterized. The resistance response signal remains nearly unchanged after 100 compressive loading cycles at a large strain of 60%. Benefiting from the design freedom of 3D printing, a practical application of the PFSS with a complex and customized structure to monitor human motion is demonstrated. These results prove that the sacrificial molding process has great potential for user-specific stretchable wearable devices.     

Highly Luminescent and Stable Green Quasi‐2D Perovskite‐Embedded Polymer Sheets by Inkjet Printing

Perovskite materials serve as promising candidates for display and lighting due to their excellent optical properties, including tunable bandgaps and efficient luminescence. However, their efficiency and stability must be improved for further application. In this work, quasi‐two‐dimensional (quasi‐2D) perovskites embedded in different polymers are prepared by inkjet printing to construct any luminescent patterns/pictures on the polymer substrates. The optimized quantum yield reaches over 65% by polyvinyl‐chloride‐based quasi‐2D perovskite composites. In addition, as‐fabricated perovskite?polymer composites with patterns show excellent resistance to abrasion, moisture, light irradiation, and chemical erosion by various solvents. Both quantum yield and lifetime are superior to those reported to date. These achievements are attributed to the introduction of the PEA⁺ cations to improve the luminance and stability of perovskite. This patterned composite can be useful for color‐conversion films with low cost and large‐scale fabrication.     

Tailoring Morphology and Structure of Inkjet‐Printed Liquid‐Crystalline Semiconductor/Insulating Polymer Blends for High‐Stability Organic Transistors

Inkjet printing of semiconducting polymers is desirable for realizing low‐cost, large‐area printed electronics. However, sequential inkjet printing methods often suffer from nozzle clogging because the solubility of semiconducting polymers in organic solvents is limited. Here, it is demonstrated that the addition of an insulating polymer to a semiconducting polymer ink greatly enhances the solubility and stability of the ink, leading to the stable ejection of ink droplets. This bicomponent blend comprising a liquid‐crystalline semiconducting copolymer, poly(didodecylquaterthiophene‐alt‐didodecylbithiazole) (PQTBTz‐C12), and an insulating commodity polymer, polystyrene, is extremely useful as a semiconducting layer in organic field‐effect transistors (OFETs), providing fine control over the phase‐separated morphology and structure of the inkjet‐printed film. Tailoring the solubility‐induced phase separation of the two components leads to a bilayer structure consisting of a polystyrene layer on the top and a highly crystalline PQTBTz‐C12 layer on the bottom. The blend film is used as the semiconducting layer in OFETs, reducing the semiconductor content to several tens of pictograms in a single device without degrading the device performance. Furthermore, OFETs based on the PQTBTz‐C12/polystyrene film exhibit much greater environmental and electrical stabilities compared to the films prepared from homo PQTBTz‐C12, mainly due to the self‐encapsulated structure of the blend film.     

Coordinatable and High Charge‐Carrier‐Mobility Water‐Soluble Conjugated Copolymers for Effective Aqueous‐Processed Polymer–Nanocrystal Hybrid Solar Cells and OFET Applications

A water‐soluble conjugated polymer (WCP) poly[(3,4‐dibromo‐2,5‐thienylene vinylene)‐co‐(p‐phenylene‐vinylene)] (PBTPV), containing thiophene rings with high charge‐carrier mobility and benzene rings with excellent solubility is designed and prepared through Wessling polymerization. The PBTPV precursor can be easily processed by employing water or alcohols as the solvents, which are clean, environmentally friendly, and non‐toxic compared with the highly toxic organic solvents such as chloroform and chlorobenzene. As a novel photoelectric material, PBTPV presents excellent hole‐transport properties with a carrier mobility of 5 × 10^?4 cm² V^?1 s^?1 measured in an organic field‐effect transistor device. By integrating PBTPV with aqueous CdTe nanocrystals (NCs) to produce the active layer of water‐processed hybrid solar cells, the devices exhibit effective power conversion efficiency up to 3.3%. Moreover, the PBTPV can form strong coordination interactions with the CdTe NCs through the S atoms on the thiophene rings, and effective coordination with other nanoparticles can be reasonably expected.     

A Tailorable Family of Elastomeric‐to‐Rigid, 3D Printable,Interbonding Polymer Networks

Soft materials with widely tailorable mechanical properties throughout the material's volume can shape the future of soft robotics and wearable electronics, impacting both consumer and defense sectors. Herein, a platform of 3D printable soft polymer networks with unprecedented tunability of stiffness of nearly three orders of magnitude (MPa to GPa) and an inherent capability to interbond is reported. The materials are based on dynamic covalent polymer networks with variable density of crosslinkers attached to prepolymer backbones via a temperature‐reversible Diels–Alder (DA) reaction. Inherent flexibility of the prepolymer chains and controllable crosslinking density enable 3D printed networks with glass transition temperatures ranging from just a few degrees to several tens of degrees Celsius. Materials with an elastomeric network demonstrate a fast and spontaneous self‐healing behavior at room temperature both in air and under water—a behavior difficult to achieve with other crosslinked materials. Reversible dissociation of DA networks at temperatures exceeding ≈120 °C allows for reprintability, while control of the stereochemistry of DA attachments enables reprogrammable shape memory behavior. The introduced platform addresses current major challenges including control of polymer interbonding, enhanced mechanical performance of printed parts, and reprocessability of 3D‐printed crosslinked materials in the absence of solvent.     

Systematic Study of Widely Applicable N‐Doping Strategy for High‐Performance Solution‐Processed Field‐Effect Transistors

A specific design for solution‐processed doping of active semiconducting materials would be a powerful strategy in order to improve device performance in flexible and/or printed electronics. Tetrabutylammonium fluoride and tetrabutylammonium hydroxide contain Lewis base anions, F^? and OH^?, respectively, which are considered as organic dopants for efficient and cost‐effective n‐doping processes both in n‐type organic and nanocarbon‐based semiconductors, such as poly[[N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene)] (P(NDI2OD‐T2)) and selectively dispersed semiconducting single‐walled carbon nanotubes by π‐conjugated polymers. The dramatic enhancement of electron transport properties in field‐effect transistors is confirmed by the effective electron transfer from the dopants to the semiconductors as well as controllable onset and threshold voltages, convertible charge‐transport polarity, and simultaneously showing excellent device stabilities under ambient air and bias stress conditions. This simple solution‐processed chemical doping approach could facilitate the understanding of both intrinsic and extrinsic charge transport characteristics in organic semiconductors and nanocarbon‐based materials, and is thus widely applicable for developing high‐performance organic and printed electronics and optoelectronics devices.     

Inkjet‐Printable Amphiphilic Polydiacetylene Precursor for Hydrochromic Imaging on Paper

Hydrochromic materials find great utility in a wide range of applications including humidity sensing and measuring the water contents of organic solvents, as well as substrates for rewritable paper and human sweat pore mapping. Herein, an inkjet printable diacetylene (DA) is described that can be transformed by UV irradiation to a hydrochromic‐conjugated polymer on conventional paper. Specifically, an amphiphilic DA that contains an ­imidazolium ion head‐group is found to be compatible with a common office inkjet printer. Various computer‐designed images are printed on paper using this substance. UV irradiation of the printed images results in the generation of blue‐colored images associated with formation of a polydiacetylene (PDA). The resolutions of the images are almost identical to those generated using a conventional black ink. Importantly, the printed images undergo a blue‐to‐red color change upon exposure to water and the hydrochromism is found to be temperature dependent. The facile color change that occurs near body ­temperatures enables use of the hydrochromic PDA‐coated paper for rapid and precise mapping of human sweat pores from fingers, palms, and feet.     

Degradable and Fully Recyclable Dynamic Thermoset Elastomer for 3D-Printed Wearable Electronics

Wearable electronics have become an important part of daily lives. However, its rapid development results in the problem of electronic waste (e-waste). Consequently, recyclable materials suitable for wearable electronics are highly sought after. In this study, a conductive recyclable composite (PFBC) is designed based on a dynamic covalently cross-linked elastomer and hierarchical hybrid nanofillers. The PFBC shows excellent wide-ranging properties including processability, elasticity, conductivity, and stability, which are superior to previous materials used for recyclable electronics, and exhibits outstanding mechanical properties and environmental tolerance including high temperature, high humidity, brine, and ethanol owing to its covalent cross-linking. Reversible dissociation of Diels–Alder networks allows for convenient processing and recycling. After three recycles, the toughness of the PFBC remained at 10.1 MJ m⁻³, which is conspicuous among the reported recyclable electronic materials. Three types of PFBC-based wearable electronics including a triboelectric nanogenerator, a capacitive pressure sensor, and a flexible keyboard, are successfully 3D printed with excellent performance. The PFBC possessed both recyclability and degradability, the combination of which provides a new way to reduce e-waste. This is the first work to recycle electronics using direct 3D printing and presents promising new design principles and materials for wearable electronics.     

Bioinspired Electro‐Thermo‐Hygro Reversible Shape‐Changing Materials by 4D Printing

Hygromorph composites are moisture‐induced shape‐changing materials that are increasingly studied to develop autonomously actuated deployable structures. The morphing mechanism is based on the high affinity for moisture and the hygroexpansive nature of at least one component, combined with a bilayer microstructure. Among available hygromorphs, those consisting of cellulosic or hydrogel material‐based actuators trigger fast responses to moisture. Their stiffness however decreases significantly with the moisture content and that restricts their potential application as soft actuators. This work proposes a novel 4D printed multistimuli‐responsive structural material based on conductive carbon reinforcements and combined with a moisture sensitive polymer. These 4D printed materials possess a microstructure that provides the capability of natural actuators like pine cones. The actuation of these functional materials could be either triggered passively by the variation of the ambient moisture, or by electroheating, with the latter leading to the control of the moisture content in initially wet samples via Joule effects. This new class of functional materials shows an increase of the actuation speed by a factor 10 compared to other existing hygromorphs with the same responsiveness. When the electrical heating is turned off, passive cooling and moisture driven actuation is triggered in a full reversible mode.     

Membrane‐Based Strategy for Efficient Ionic Liquids/Water Separation Assisted by Superwettability

Ionic liquids (ILs) acting as new functional solvents have significant impact in both synthetic and materials chemistry. However, the usage of volatile organic solvents in both synthesis and recycling of ILs usually imposes environmental issues. In this study, according to intrinsic wetting threshold theory, a membrane‐based approach assisted by superwettability is developed for efficient, convenient, and economical purification of water‐immiscible ILs. By precisely tailoring surface energy, the porous membrane is capable of hydrophobicity and superILphilicity (defined as IL contact angle close to zero), selectively allowing ILs to pass through. This kind of functional membrane can not only separate IL/water mixtures, but also IL/water systems containing inorganic salts, organic compounds, amino acids, and proteins.     

Printed and Electrochemically Gated,High‐Mobility,Inorganic Oxide Nanoparticle FETs and Their Suitability for High‐Frequency Applications

Solution‐processed or printed n‐channel field‐effect transistors (FETs) with high performance are not reported very often in the literature due to the scarcity of high‐mobility n‐type organic semiconductors. On the other hand, low‐temperature processed n‐channel metal oxide semiconductor (NMOS) transistors from electron conducting inorganic‐oxide nanoparticles show reduced‐performance and low mobility because of large channel roughness at the channel‐dielectric interface. Here, a method to produce ink‐jet printed high performance NMOS transistor devices using inorganic‐oxide nanoparticles as the transistor channel in combination with a 3D electrochemical gating (EG) via printed composite solid polymer electrolytes is presented. The printed FETs produced show a device mobility value in excess of 5 cm² V^?1 s^?1, even though the root mean square (RMS) roughness of the nanoparticulate channel exceeds 15 nm. Extensive studies on the frequency dependent polarizability of composite polymer electrolyte capacitors show that the maximum attainable speed in such printed, long channel transistors is not limited by the ionic conductivity of the electrolytes. Therefore, the approach of combining printable, high‐quality oxide nanoparticles and the composite solid polymer electrolytes, offers the possibility to fully utilize the large mobility of oxide semiconductors to build all‐printed and high‐speed devices. The high polarizability of printable polymer electrolytes brings down the drive voltages to ≤1 V, making such FETs well‐suited for low‐power, battery compatible circuitry.