Mechanically robust, self-reporting and healable polyurethane elastomers by incorporating symmetric/asymmetric chain extenders.

Self-healing elastomers usually show poor mechanical properties and environmental stability, and they cannot self-report mechanical/chemical damage. Herein, an innovative design strategy is reported that combines symmetric/asymmetric chain extenders to create large yet disordered hard domains within polyurethane (PU) elastomers, enabling the integration of mechanical robustness and self-reporting and self-healing capabilities to overcome both mechanical and chemical damage. Specifically, large yet disordered hard domains were created by governing the molar contents of asymmetric fluorescent 2-(4-aminophenyl)-5-aminobenzimidazole (PABZ) and symmetric 4-aminophenyl disulfide (APDS). Such a structural feature led to a small free-volume fraction, prominent strain-induced crystallization (SIC), and high energy of dissipation, enabling the PU elastomer to display outstanding mechanical strength (60.7 MPa) and toughness (177.9 MJ m-3). Meanwhile, the loose stacking of disordered hard domains imposed small restriction on network chains and imparted the network with high relaxation dynamics, leading to high healing efficiency (97.8%). More importantly, the fluorescence intensity was stimulus-responsive and thus the PU elastomer could self-report mechanical/chemical damage and healing processes. The PU elastomer also showed potential application prospects in information encoding and encryption. Furthermore, selecting polydimethylsiloxane as one of the soft segments could effectively endow the PU elastomer with intrinsic hydrophobicity. Therefore, this work provides valuable guidance for designing multi-functional materials with anti-counterfeiting, self-reporting, and healing properties as well as high mechanical properties and hydrophobicity.

Mechanical Robust, Self-Healable Polyurethane Elastomer Enabled by Hierarchical Hydrogen Bonds and Disulfide Bonds.

The fabrication of mechanically robust and self-healing polymeric materials remains a formidable challenge. To address the drawbacks, a core strategy is proposed based on the dynamic hard domains formed by hierarchical hydrogen bonds and disulfide bonds. The dynamic hard domains dissipate considerable stress energy during stretching. Meanwhile, the synergistic effect of hierarchical hydrogen bonds and disulfide bonds greatly enhances the relaxation dynamics of the PU network chains, thus accelerating network reorganization. Therefore, this designed strategy effectively solves the inherent drawback between cohesive energy and relaxation dynamics of the PU network. As a result, the PU elastomer has excellent mechanical properties (9.9 MPa and 44.87 MJ/m3) and high self-healing efficiency (96.2%). This approach provides a universal but valid strategy to fabricate high-performance self-healing polymeric materials. Meanwhile, such materials can be extended to emerging fields such as flexible robotics and wearable electronics.

Tough and Robust Metallosupramolecular Hydrogels Enabled by Ti3C2Tx MXene Nanosheets.

Recently, many tough synthetic hydrogels have been created as promising candidates in fields such as smart electronic devices. In this paper, we propose a simple strategy to construct tough and robust hydrogels. Two-dimensional Ti3C2Tx MXene nanosheets and metal ions were introduced into poly(acrylamide-co-acrylic acid) hydrogels, the MXene nanosheets acted as multifunctional cross-linkers and effective stress-transfer centers, and physical cross-links were formed between Fe3+ and carboxylic acid. Under deformation, the coordination interactions exhibit reversible dissociation and reorganization properties, suggesting a novel mechanism of energy dissipation and stress redistribution. The design enabled the hydrogel to exhibit outstanding and balanced mechanical properties (tensile strength of up to 5.67 MPa and elongation at break of up to 508%). This study will facilitate the diverse applications of metallosupramolecular hydrogels.

Bio-inspired nacre-like composites with excellent mechanical properties, gas-barrier function and fire-retardant performances based on self-assembly between hyperbranched poly(amido amine)s and montmorillonite.

The fabrication of mechanically robust multifunctional nanocomposite (NC) films using simple but effective strategies is a long-term challenge. Inspired by natural nacre, we designed and fabricated high-performance nacre-like NC films (Na-MTM/HBP) through the self-assembly of the hyperbranched poly(amido amine) (HBP) and montmorillonite (Na-MTM) using a vacuum filtration approach. The optimal Na-MTM/HBP NC film shows excellent mechanical strength (106 MPa), which can be attributed to the formation of numerous hydrogen bonds and the electrostatic interactions between hyperbranched HBP and Na-MTM nanosheets. Such films also exhibit excellent gas barrier and fire-fire-retardant owing to the high aspect ratio of the Na-MTM nanosheets. In this work, a class of high-performance NC films exhibiting good mechanical, gas barrier, and flame retardancy properties have been developed. These NC films have great potential in packing or coating materials.

Self-Healing, Reconfigurable, Thermal-Switching, Transformative Electronics for Health Monitoring.

Soft, deformable electronic devices provide the means to monitor physiological information and health conditions for disease diagnostics. However, their practical utility is limited due to the lack of intrinsical thermal switching for mechanically transformative adaptability and self-healing capability against mechanical damages. Here, the design concepts, materials and physics, manufacturing approaches, and application opportunities of self-healing, reconfigurable, thermal-switching device platforms based on hyperbranched polymers and biphasic liquid metal are reported. The former provides excellent self-healing performance and unique tunable stiffness and adhesion regulated by temperature for the on-skin switch, whereas the latter results in liquid metal circuits with extreme stretchability (>900%) and high conductivity (3.40 × 104  S cm-1 ), as well as simple recycling capability. Triggered by the increased temperature from the skin surface, a multifunctional device platform can conveniently conform and strongly adhere to the hierarchically textured skin surface for non-invasive, continuous, comfortable health monitoring. Additionally, the self-healing and adhesive characteristics allow multiple multifunctional circuit components to assemble and completely wrap on 3D curvilinear surfaces. Together, the design, manufacturing, and proof-of-concept demonstration of the self-healing, transformative, and self-assembled electronics open up new opportunities for robust soft deformable devices, smart robotics, prosthetics, and Internet-of-Things, and human-machine interfaces on irregular surfaces.

Mechanically Robust Dual-Crosslinking Elastomer Enabled by a Facile Self-Crosslinking Approach.

We propose a simple but rapid strategy to fabricate self-crosslinked dual-crosslinking elastomers (SCDCEs) with high mechanical properties. The SCDCEs are synthesized through one-pot copolymerization of Butyl acrylate (BA), acrylic amide (AM), and 3-Methacryloxypropyltrimethoxysilane (MEMO). Both the amino group on AM and the methoxy group on MEMO can be self-crosslinked after polymerization to form a dual-network crosslink consisting of hydrogen bonds crosslink and Si-O-Si covalent bonds crosslink. The SCDC endow optimal elastomer with high mechanical properties (the tensile strength is 6MPa and elongation at break is 490%) as the hydrogen bonds crosslink can serve as sacrificial construction to dissipate stress energy, while covalent crosslinking networks can ensure the elasticity and strength of the material. These two networks also contribute to the recoverability of the elastomers, leading them to recover their original shape and mechanical properties after being subjected to deformation in a short time.

Tough and Resilient Hydrogels Enabled by a Multifunctional Initiating and Cross-Linking Agent.

Many high-strength hydrogels have been developed in recent years; however, few of them are both tough and resilient, and their intrinsic paradoxical nature makes designing a gel with both high toughness and high resilience a great challenge. To address this problem, we introduced both N,N,N,N-pentamethyldiethylenetriamine (PA) and N,N-methylenebisacrylamide (MBA) into polyacrylamide hydrogel networks to construct an entangled network that contains chemically cross-linked chains and branched chains simultaneously. The entanglements of branched chains can act as a physical cross-linking point to uniformly disperse stress on molecular chains, and chemical cross-linking ensures the stability of the hydrogel network. The increase in the number and length of branched chains is able to achieve an enhancement in strength while the slip of the entangled polymer chains can effectively achieve energy dissipation and can improve the toughness of the gel. Moreover, the resultant hydrogels exhibit an excellent resilience (>98%). Therefore, high toughness and resilience are achieved simultaneously. In addition, we also investigated the initiation mechanism of PA. This strategy creates a new way for the preparation of next-generation high toughness and high resilience hydrogel-based materials, which have promising applications in wearable, flexible strain/pressure sensors.

A Degradable and Self-Healable Vitrimer Based on Non-isocyanate Polyurethane.

Developing degradable and self-healable elastomers composed of reusable resources is of great value but is rarely reported because of the undegradable molecular chains. Herein, we report a class of degradable and self-healable vitrimers based on non-isocyanate polyurethane elastomer. Such vitrimers are fabricated by copolymerizing bis(6-membered cyclic carbonate) and amino-terminated liquid nitrile rubber. The networks topologies can rearrange by transcarbonation exchange reactions between hydroxyl and carbonate groups at elevated temperatures; as such, vitrimers after reprocessing can recover 82.9-95.6% of initial tensile strength and 59-131% of initial storage modulus. Interestingly, the networks can be hydrolyzed and decarbonated in the strong acid solution to recover 75% of the pure di(trimethylolpropane) monomer. Additionally, the elastomer exhibits excellent self-healing efficiency (~88%) and fracture strain (~1,200%) by tuning the monomer feeding ratio. Therefore, this work provides a novel strategy to fabricate the sustainable elastomers with minimum environmental impact.