Supramolecular polymer networks (SPNs), crosslinked by noncovalent bonds, have emerged as reorganizable and recyclable polymeric materials with unique functionality. However, poor stability is an imperative challenge faced by SPNs, because SPNs are susceptible to heat, water, and/or solvents due to the dynamic and reversible nature of noncovalent bonds. Herein, the design of a noncovalent cooperative network (NCoN) to simultaneously stabilize and reinforce SPNs is reported, resulting in an ultrastable, superrobust, and recyclable SPN. The NCoN is constructed by multiplying the H-bonding sites and tuning the conformation/geometry of the H-bonding segment to optimize the multivalence cooperativity of H-bonds. The rationally designed H-bonding segment with high conformational compliance favors the formation of tightly packed H-bond arrays comprising higher-density and stronger H-bonds. Consequently, the H-bonded crosslinks in the NCoN display a covalent crosslinking effect but retain on-demand dynamics and reversibility. The resultant ultrastable SPN not only displays remarkable resistance to heat up to 120 °C, water soaking, and a broad spectrum of solvents, but also possesses a superhigh true stress at break (1.1â GPa) and an ultrahigh toughness (406â MJ m-3 ). Despite the covalent-network-like stability, the SPN is recyclable through activating its reversibility in a high-polarity solvent heated to a threshold temperature.
Bioinspired hydrogels have demonstrated multiple superiorities over traditional wound dressings for wound healing applications. However, the fabrication of bioinspired hydrogel-based wound dressings with desired functionalities always requires multiple successive steps, time-consuming processes, and/or sophisticated protocols, plaguing their clinical applications. Here, a facile one-pot strategy is developed to prepare a skin-inspired multifunctional hydrogel within 30 min by incorporating elastin (an essential functional component of the dermal extracellular matrix), tannic acid, and chitosan into the covalently cross-linked poly(acrylamide) network through noncovalent interactions. The resulting hydrogel exhibits a Young's modulus (ca. 36 kPa) comparable to that of human skin, a high elongation-at-break (ca. 1550%), a satisfactory tensile strength (ca. 61 kPa), and excellent elastic self-restorability, enabling the hydrogel to synchronously and conformally deform with human skin when used as wound dressings. Importantly, the hydrogel displays a self-adhesive property to skin tissues with an appropriate bonding strength (ca. 55 kPa measured on intact porcine skin), endowing the hydrogel with the ability to rapidly self-adhere to intact human skin, sealing the wound surface and also easily being removed without residue left or trauma caused to the skin. The hydrogel also possesses remarkable antibacterial activity, antioxidant capability, and hemocompatibility. All of these collective beneficial properties enable the hydrogel to significantly accelerate the wound healing process, outperforming the commercial wound dressings.
The development of stable and biocompatible soft ionic conductors, alternatives to hydrogels and ionogels, will open up new avenues for the construction of stretchable electronics. Here, a brand-new design, encapsulating a naturally occurring ionizable compound by a biocompatible polymer via high-density hydrogen bonds, resulting in a solvent-free supramolecular ion-conductive elastomer (SF-supra-ICE) that eliminates the dehydration problem of hydrogels and possesses excellent biocompatibility, is reported. The SF-supra-ICE with high ionic conductivity (>3.3 × 10-2 S m-1 ) exhibits skin-like softness and strain-stiffening behaviors, excellent elasticity, breathability, and self-adhesiveness. Importantly, the SF-supra-ICE can be obtained by a simple water evaporation step to solidify the aqueous precursor into a solvent-free nature. Therefore, the aqueous precursor can act as inks to be painted and printed into customized ionic tattoos (I-tattoos) for the construction of multifunctional on-skin bioelectronics. The painted I-tattoos exhibit ultraconformal and seamless contact with human skin, enabling long-term and high-fidelity recording of various electrophysiological signals with extraordinary immunity to motion artifacts. Human-machine interactions are achieved by exploiting the painted I-tattoos to transmit the electrophysiological signals of human beings. Stretchable I-tattoo electrode arrays, manufactured by the printing method, are demonstrated for multichannel digital diagnosis of the health condition of human back muscles and spine.
Elastomers , Tattooing , Humans , Elastomers/chemistry , Solvents , Skin , Hydrogels
The performance of any engineering material is naturally limited by its structure, and while each material suffers from one or multiple shortcomings when considered for a particular application, these can be potentially circumvented by hybridization with other materials. By combining organic crystals with MXenes as thermal absorbers and charged polymers as adhesive counter-ionic components, we propose a simple access to flexible hybrid organic crystal materials that have the ability to mechanically respond to infrared light. The ensuing hybrid organic crystals are durable, respond fast, and can be cycled between straight and deformed state repeatedly without fatigue. The point of flexure and the curvature of the crystals can be precisely controlled by modulating the position, duration, and power of thermal excitation, and this control can be extended from individual hybrid crystals to motion of ordered two-dimensional arrays of such crystals. We also demonstrate that excitation can be achieved over very long distances (>3 m). The ability to control the shape with infrared light adds to the versatility in the anticipated applications of organic crystals, most immediately in their application as thermally controllable flexible optical waveguides for signal transmission in flexible organic electronics.
The capability of stimulated response by mechanical deformation to induce motion or actuation is the foundation of lightweight organic, dynamic materials for designing light and soft robots. Various biomimetic soft robots are constructed to demonstrate the vast versatility of responses and flexibility in shape-shifting. We now report that the integration of organic molecular crystals and polymers brings about synergistic improvement in the performance of both materials as a hybrid materials class, with the polymers adding hygroresponsive and thermally responsive functionalities to the crystals. The resulting hybrid dynamic elements respond within milliseconds, which represents several orders of magnitude of improvement in the time response relative to some other type of common actuators. Combining molecular crystals with polymers brings crystals as largely overlooked materials much closer to specific applications in soft (micro)robotics and related fields.
Development of closed-loop chemically recyclable plastics (CCRPs) that can be widely used in daily life can be a fundamental solution to the global plastic waste crisis. Hence, it is of great significance to develop easy-to-recycle CCRPs that possess superior or comparable material properties to the commodity plastics. Here, a novel dual crosslinked CCRP, namely, supramolecular covalent adaptable networks (supra-CANs), is reported, which not only displays mechanical properties higher than the strong and tough commodity polycarbonate, but also exhibits excellent solvent resistance as thermosets. The supra-CANs are constructed by introducing reversible noncovalent crosslinks into the dynamic covalent polymer networks, resulting in highly stiff and strong thermosets that also exhibit thermoplastic-like ductile and tough behaviors as well as reprocessability and rehealability. In great contrast, the analogs that do not have noncovalent crosslinks (CANs) show elastomeric properties with significantly decreased mechanical strength. Importantly, the developed supra-CANs and CANs can be converted back into the initial monomers in high yields and purity at room temperature, even with additives, which enables the sustainable polymer-monomer-polymer circulation. This work provides new design principles for high-performance chemically recyclable polymers as sustainable substitutes for the conventional plastics.
Hybrid materials capitalize on the properties of individual materials to attain a specific combination of performance assets that is not available with the individual components alone. We describe a straightforward approach to preparation of sandwich-type hybrid dynamic materials that combine metals as electrically conductive components and polymers as bending, momentum-inducing components with flexible organic crystals as mechanically compliant and optically transducive medium. The resulting hybrid materials are conductive to both electricity and light, while they also respond to changes in temperature by deformation. Depending on the metal, their conductivity ranges from 7.9 to 21.0 S µmâ1. The elements respond rapidly to temperature by curling or uncurling in about 0.2 s, which in one typical case corresponds to exceedingly fast deformation and recovery rates of 2187.5° sâ1 and 1458.3° sâ1, respectively. In cyclic operation mode, their conductivity decreases less than 1% after 10,000 thermal cycles. The mechanothermal robustness and dual functionality favors these materials as candidates for a variety of applications in organic-based optics and electronics, and expands the prospects of application of organic crystals beyond the natural limits of their dynamic performance.
With the rapid development of soft electronics in the era of Internet of Everything (IoE), electrical conductors with stretchability, the indispensable components of soft electronics, have gained new opportunities and also faced increasing challenges. According to the principles of electrical conductivity, stretchable electrical conductors can be divided into electronic conductors and ionic conductors. Different from the stretchable electronic conductors derived from stretchable polymeric matrices integrated with electronically conductive fillers, stretchable ionic conductors are constructed by embedding mobile ions into the crosslinked polymer networks. Therefore, stretchable ionic conductors have received extensive attention and in-depth research in the past decade, thanks to their intrinsic stretchability and electrical conductivity. This review systematically summarizes the achievements on the different categories of stretchable ionic conductors (e.g., hydrogels, ionogels, and liquid-free ion-conductive elastomers), in terms of their design, fabrication, properties, and applications. The advantages and limitations of the different types of stretchable ionic conductors are discussed. Outlooks are also provided to envision the remaining challenges for the further development and practical applications of stretchable ionic conductors. It is expected to arouse inspirations for the design and fabrication of new and high-performance stretchable ionic conductors and advanced soft electronics for the IoE era.
Elastic organic crystals are the materials foundation of future lightweight flexible electronic, optical and sensing devices, yet precise control over their deformation has not been accomplished. Here, we report a general non-destructive approach to remote bending of organic crystals. Flexible organic crystals are coupled to magnetic nanoparticles to prepare hybrid actuating elements whose shape can be arbitrarily and precisely controlled simply by using magnetic field. The crystals are mechanically and chemically robust, and can be flexed precisely to a predetermined curvature with complete retention of their macroscopic integrity at least several thousand times in contactless mode, in air or in a liquid medium. These crystals are used as optical waveguides whose light output can be precisely and remotely controlled by using a permanent magnet. This approach expands the range of applications of flexible organic crystals beyond the known limitations with other methods for control of their shape, and opens prospects for their direct implementation in flexible devices such as sensors, emitters, and other (opto)electronics.
Applications in extreme conditions, such as those encountered in space exploration, require lightweight materials that can retain their elasticity in extremely cold environments. However, cryogenic treatment of most soft polymeric and elastomeric materials results in complete loss of their ability for elastic flow, whereby such materials that are normally ductile become stiff, brittle, and prone to cracking. Here, a facile method for preparation of hybrid organic crystalline materials that are not only cryogenically robust but are also capable of large, recoverable, and reversible deformation at low temperatures is reported. To that end, flexible organic crystals are first mechanically reinforced by a polymer coating and combined with a thermally responsive polymer. The resulting hybrid materials respond linearly and reversibly to temperatures from -15 to -120 °C without fatigue in air as well as in cold vacuum. The approach proposed here not only circumvents one of the main drawbacks that are inherent to the amorphous nature and has thus far limited the applications of polymeric materials at low temperatures, but it also provides a cost-effective access to a myriad of lightweight sensing, electronic, optical or actuating devices that can operate in low-temperature environmental settings.
Reshaping of elongated organic crystals that can be used as semiconductors, waveguides or soft robotic grippers by application of force or light is now a commonplace, however mechanical response of organic crystals to changes in humidity has not been accomplished yet. Here, we report a universal approach to instigating a humidity response into elastically bendable organic crystals that elicits controllable deformation with linear response to aerial humidity while retaining their physical integrity entirely intact. Hygroresponsive bilayer elements are designed by mechanically coupling a humidity-responsive polymer with elastic molecular crystals that have been mechanically reinforced by a polymer coating. As an illustration of the application of these cladded crystalline actuators, they are tested as active optical transducers of visible light where the position of light output can be precisely controlled by variations in aerial humidity. Within a broader context, the approach described here provides access to a vast range of mechanically robust, lightweight hybrid hygroresponsive crystalline materials.
Solar anti-/deicing can solve icing problems by converting sunlight into heat. One of the biggest problems, which has long been plaguing the design of solar anti-/deicing surfaces, is that photothermal materials are always lightproof and appear black, because of the mutual exclusiveness between generating heat and retaining transparency. Herein, a highly transparent and scalable solar anti-/deicing surface is reported, which enables the coated glass to exhibit high transparency (>77% transmittance at 550 nm) and meanwhile causes a >30 °C surface temperature increase relative to the ambient environment under 1.0 sun illumination. Such a transparent anti-/deicing surface can be fabricated onto a large class of substrates (e.g., glass, ceramics, metals, plastics), by applying a solid omniphobic slippery coating onto layer-by-layer-assembled ultrathin MXene multilayers. Hence, the surface possesses a self-cleaning ability to shed waterborne and oil-based liquids thanks to residue-free slipping motion. Passive anti-icing and active deicing capabilities are, respectively, obtained on the solar thermal surface, which effectively prevents water from freezing and simultaneously melts pre-formed ice and thick frost. The self-cleaning effect enables residue-free removal of unfrozen water and interfacially melted ice/frost to boost the anti-/deicing efficiency. Importantly, the surface is capable of self-healing under illumination to repair physical damage and chemical degradation.
Flexible perovskite solar cells (FPSCs) have attracted great attention due to their advantageous traits such as low cost, portability, light-weight, etc. However, mechanical stability is still the weak point in their practical application. Herein, we prepared efficient FPSCs with remarkable mechanical stability by a dynamic thermal self-healing effect, which can be realized by the usage of a supramolecular adhesive. The supramolecular adhesive, which was obtained by random copolymerization of acrylamide and n-butyl acrylate, is amphiphilic, has a proper glass transition temperature and a high density of hydrogen-bond donors and receptors, providing the possibility of thermal dynamic repair of mechanical damage in FPSCs. The adhesive also greatly improves the leveling property of the precursor solution on the hydrophobic poly[bis(4-phenyl)(2,4,6-trimethylphenyl)]amine (PTAA) surface. PSCs containing this adhesive achieve more than a 20 % power conversion efficiency (PCE) on flexible substrates and a 21.99 % PCE on rigid substrates (certified PCE of 21.27 %), with improved electron mobility and reduced defect concentration.
Spider silk is one of the most robust natural materials, which has extremely high strength in combination with great toughness and good elasticity. Inspired by spider silk but beyond it, a healable and recyclable supramolecular elastomer, possessing superhigh true stress at break (1.21 GPa) and ultrahigh toughness (390.2 MJ m-3 ), which are, respectively, comparable to and ≈2.4 times higher than those of typical spider silk, is developed. The elastomer has the highest tensile strength (ultimate engineering stress, 75.6 MPa) ever recorded for polymeric elastomers, rendering it the strongest and toughest healable elastomer thus far. The hyper-robust elastomer exhibits superb crack tolerance with unprecedentedly high fracture energy (215.2 kJ m-2 ) that even exceeds that of metals and alloys, and superhigh elastic restorability allowing dimensional recovery from elongation over 12 times. These extraordinary mechanical performances mainly originate from the meticulously engineered hydrogen-bonding segments, consisting of multiple acylsemicarbazide and urethane moieties linked with flexible alicyclic hexatomic spacers. Such hydrogen-bonding segments, incorporated between extensible polymer chains, aggregate to form geometrically confined hydrogen-bond arrays resembling those in spider silk. The hydrogen-bond arrays act as firm but reversible crosslinks and sacrificial bonds for enormous energy dissipation, conferring exceptional mechanical robustness, healability, and recyclability on the elastomer.
Recently, luminescent organic crystals have been widely studied as new optoelectronic materials. However, corrosion and dissolution of organic crystals by solvents have always been a great challenge for the application of organic crystals in various fields. In this work, we propose a general method of fabricating a solvent-resistant coating to prevent organic crystals from being corroded or dissolved by organic solvents. The coatings involved layer-by-layer assembly of poly(diallyldimethylammonium) (PDDA) and poly(styrenesulfonate) (PSS) onto crystals, followed by immersing the coated crystals into polyvinyl alcohol (PVA) aqueous solutions for 2â minutes. The coated crystals can remain intact over 24â h in common organic solvents without being damaged and even insoluble in dichloromethane for 5â days. Moreover, the thin and transparent coatings have little effect on the optical properties of crystals which still have excellent optical waveguide performance with the coatings.
The fabrication of highly durable skin-mimicking sensors remains challenging because of the unavoidable fatigue and physical damage that sensors are subjected to in practical applications. In this study, ultra-durable ionic skins (I-skins) with excellent healability and high sensitivity are fabricated by impregnating ionic liquids (ILs) into a mechanically robust poly(urea-urethane) (PU) network. The PU network is composed of crystallized poly(ε-caprolactone) and flexible poly(ethylene glycol) that are dynamically cross-linked with hindered urea bonds and hydrogen bonds. Such a design endows the resultant ionogels with high mechanical strength, good elasticity, Young's modulus similar to that of natural skin, and excellent healability. The ionogel-based I-skins exhibit a high sensitivity to a wide range of strains (0.1-300%) and pressures (0.1-20 kPa). Importantly, the I-skins show a highly reproducible electrical response over 10 000 uninterrupted strain cycles. The sensing performance of the I-skins stored in open air for 200 days is almost the same as that of the freshly prepared I-skin. The fractured I-skins can be easily healed by heating at 65 °C that restores their original ultra-durable sensing performance. The long-term durability of the I-skins is attributed to the combination of non-volatility of the ILs, excellent healability, and well-designed mechanical properties.
To build a sustainable society, it is of significant importance but highly challenging to develop remalleable, healable, and biodegradable polymeric materials with integrated high strength and high toughness. Here, we report a superstrong and ultratough sustainable supramolecular polymeric material with a toughness of ca. 282.3 J g-1 (395.2 MJ m-3) in combination with a tensile strength as high as ca. 104.2 MPa and a Young's modulus of ca. 3.53 GPa. The toughness is even higher than that of the toughest spider silk (ca. 354 MJ m-3) ever found in the world, while the material also exhibits a superior tensile strength over most engineering plastics. This material is fabricated by topological confinement of the biodegradable linear polymer of poly(vinyl alcohol) (PVA) via the naturally occurring dendritic molecules of tannic acid (TA) based on high-density hydrogen bonds. Simply blending TA and PVA in aqueous solutions at acidic conditions leads to the formation of TA-PVA complexes as precipitates, which can be processed into dry TA-PVA composite products with desired shapes via the compression molding method. Compared to the conventional solution casting method for the fabrication of PVA-based thin films, the as-developed strategy allows large-scale production of bulk TA-PVA composites. The TA-PVA composites consist of interpenetrating three-dimensional supramolecular TA-PVA clusters. Such a structural feature, revealed by computational simulations, is crucial for the integrated superhigh strength and ultrahigh toughness of the material. The biodegradable TA-PVA composites are remalleable for multiple generations of recycling and healable after break, at room temperature, by the assistance of water to activate the reversibility of the hydrogen bonds. The TA-PVA composites show high promise as sustainable substitutes for conventional plastics because of their remalleability, healability, and biodegradability. The integrated superhigh strength and ultrahigh toughness of the TA-PVA composites ensure their high reliability and broad applicability.
It is highly desirable to develop reversible and easy-release adhesives with high bonding strength for a broad range of substrates, while the adhesion of low-surface-energy materials (e.g., polytetrafluoretyhylene, PTFE) is challenging. Herein, a substrate-independent ionogel adhesive is developed by blending an ionic liquid with the copolymer bearing charged segments. By regulating the viscoelastic properties of the ionogel, the adhesive and cohesive strength of the ionogel can be well balanced to maximize the bonding strength for different substrates. The as-developed ionogel exhibits high bonding strength (>0.3 MPa) for PTFE, plastics, metal, wood, and glass, because the variety of functional groups in the ionogel can form various supramolecular interactions with different substrates. The ionogel also exhibits reversible, easy-release, and reusable properties for multiple times of bonding and on-demand debonding without leaving obvious residues on the substrates. The ionogel has high potential for practical applications as temporal adhesives with high bonding strength.
Adhesives , Polymers , Materials Testing
In the present work, we demonstrate a bidirectional substitution between perfluorooctanoate (PFO) surfactants and polyanions throughout the pre-assembled polyelectrolyte multilayers (PEMs) for a rapid modulation of surface wettability between amphiphobicity and amphiphilicity. Upon incubation of the PEMs made of alternating deposition of poly(diallyldimethylammonium) (PDDA) and poly(styrenesulfonate) (PSS) in PFO solutions at concentrations above or around its critical micelle concentration, the majority (ca. >75%) of PSS molecules throughout the PDDA/PSS PEMs can be substituted by PFO anions within 10 s, generating PFO-substituted PDDA/PSS (PFO-PDDA/PSS) films. This effective substitution of PSS polyanions in PDDA/PSS PEMs by PFO anions is suggested by the mechanism that the stability of PDDA/PFO complexes is higher than that of PDDA/PSS PEMs. Furthermore, PFO anions all the way through the PFO-PDDA/PSS films can be reversibly substituted by PSS polyanions, while the substitution efficiency depends on the ionic strength of the PSS solutions. The processes of bidirectional and reversible substitution between PFO anions and PSS polyanions throughout the PDDA/PSS films can be repeated at least 10 times accompanied with a negligible change in the film thickness and surface morphology. The surface wettability study reveals that the PFO-PDDA/PSS films are amphiphobic with water and oil contact angles (CAs) of 114 ± 2 and 64 ± 2°, respectively, while PSS-substituted PFO-(PDDA/PSS) films are amphiphilic with water and oil CAs of 6 ± 1 and 0°, respectively. These novelties of the films enable switchable surface wettability simply by dipping the PDDA/PSS film-coated objects into PFO solutions for 2 s or PSS solutions for 30 s.
High-performance solid-state electrolytes with healability to repair mechanical damages are important for the fabrication of Li-ion batteries (LIBs) with enhanced safety and prolonged service life. In this study, we present the fabrication of healable, highly conductive, flexible, and nonflammable ionogel electrolytes for use in LIBs by loading ionic liquids and Li salts within a hydrogen-bonded supramolecular poly(ionic liquid) copolymer network. The ionogel electrolytes exhibit ionic conductivities as high as 10-3 S/cm, which is comparable to the conventional liquid electrolytes. The Li/LiFePO4 battery assembled with the ionogel membrane exhibits excellent cycling performance and delivers a steady high discharge capacity of 147.5 mA h g-1 and Coulombic efficiency of 99.7% after 120 cycles at the charge/discharge rate of 0.2 C. Importantly, the ionogel membranes can heal damages outside or inside a battery because of the reversible nature of the supramolecular interactions between the components. The damaged ionogel membranes after being healed can effectively restore the original performance of the LIBs.
