Autonomous Self-healing Ability Research Articles

Polyfunctional and Multisensory Bio-Ionoelastomers Enabled by Covalent Adaptive Networks With Hierarchically Dynamic Bonding.

Developing versatile ionoelastomers, the alternatives to hydrogels and ionogels, will boost the advancement of high-performance ionotronic devices. However, meeting the requirements of bio-derivation, high toughness, high stretchability, autonomous self-healing ability, high ionic conductivity, reprocessing, and favorable recyclability in a single ionoelastomer remains a challenging endeavor. Herein, a dynamic covalent and supramolecular design, lipoic acid (LA)-based dynamic covalent ionoelastomer (DCIE), is proposed via melt building covalent adaptive networks with hierarchically dynamic bonding (CAN-HDB), wherein lithium bonds aid in the dissociation of ions and the integration of dynamic disulfide metathesis, lithium bonds, and binary hydrogen bonds enhances the mechanical performances, self-healing capability, reprocessing, and recyclability. Therefore, the trade-off among mechanical versatility, ionic conductivity, self-healing capability, reprocessing, and recyclability is successfully handled. The obtained DCIE demonstrates remarkable stretchability (1011.7%), high toughness (3877kJm-3), high ionic conductivity (3.94×10-4Sm-1), outstanding self-healing capability, reprocessing for 3D printing, and desirable recyclability. Significantly, the selective ion transport endows the DCIE with multisensory feature capable of generating continuous electrical signals for high-quality sensations towards temperature, humidity, and strain. Coupled with the straightforward methodology, abundant availability of LA and HPC, as well as multifunction, the DCIEs present new concept of advanced ionic conductors for developing soft ionotronics.

Proton Hydrogel-Based Supercapacitors with Rapid Low-Temperature Self-Healing Properties.

Hydrogel-based supercapacitors are an up-and-coming candidate for safe and portable energy storage. However, it is challenging for hydrogel electrolytes to achieve high conductivity and rapid self-healing at subzero temperatures because the movements of polymer chains and the reconstruction capability of broken dynamic bonds are limited. Herein, a highly conductive proton polyacrylamide-phytic acid (PAAm-PA) hydrogel electrolyte with rapid and autonomous self-healing ability and excellent adhesion over a wide temperature range is developed. PA, as a proton donor center, endows the hydrogels with high conductivity (102.0 mS cm-1) based on the Grotthuss mechanism. PA can also prevent the crystallization of water and form multiple reversible hydrogen bonds in the polymer network, which solves the dysfunction of self-healing hydrogels in a cryogenic environment. Accordingly, the hydrogel electrolytes demonstrate fast low-temperature self-healing ability with a self-healing efficiency of 79.4% within 3 h at -20 °C. In addition, the hydrogel electrolytes present outstanding adhesiveness on electrodes due to the generation of hydrogen bonds between PA and activated carbon electrodes. As a result, the integrated hydrogel-based supercapacitors with tight bonding electrode/electrolyte interface deliver a 139.5 mF cm-2 specific capacitance at 25 °C. Moreover, the supercapacitors display superb self-healing ability, achieving 92.1% of capacitance recovery after three cutting-healing cycles at -20 °C. Furthermore, the supercapacitors demonstrate only 6.4% capacitance degradation after 5000 charging-discharging cycles at -20 °C. This work provides a roadmap for designing all-in-one flexible energy storage devices with excellent self-healing ability over a wide temperature range.

Ultrastretchable Self-Healing Paampsa/PANI/PA Polymer Complex as a Piezoresistive Sensor

Wearable sensors, stretchable electronics, and many soft robotics materials must have a sufficiently high balance of conductivity, stretchability, and robustness. Intrinsically conductive polymers offer a critical step toward improving wearable sensor materials due to their tunable conductivity, soft/compliant nature, and ability to complex with other synergistic molecules (i.e., polyacids, small molecule dopants). This work demonstrates a new regenerative polymer complex composed of poly(2-acrylamido-2-methyl-1-propanesulfonic acid), polyaniline, and phytic acid as a skin-like electronic material. It exhibits ultrahigh stretchability (1935%), repeatable autonomous self-healing ability (repeating healing efficiency >98%), quadratic response to strain (R2 > 0.9998), and linear response to flexion bending (R2 > 0.9994), outperforming current reported wearable strain sensors. While nanofillers typically increase conductivity at the expense of mechanical properties, here we show an increase in both conductivity and mechanical properties when silver nanowires are added, forming a polymer nanocomposite with high electronic sensitivity, unprecedented mechanical properties (a maximum strain of 4693% at ambient humidity; ~52 RH%), and repeatable, autonomous self-healing efficiencies of greater than 98%.

Quadruple H-Bonding and Polyrotaxanes Dual Cross-linking Supramolecular Elastomer for High Toughness and Self-healing Conductors.

Tough and self-healable substrates can enable stretchable electronics long service life. However, for substrates, it still remains a challenge to achieve both high toughness and autonomous self-healing ability at room temperature. Herein, a strategy by using the combined effects between quadruple H-bonding and slidable cross-links is proposed to solve the above issues in the elastomer. The elastomer exhibits high toughness (77.3 MJ m-3 ), fracture energy (≈127.2 kJ m-2 ), and good healing efficiency (91 %) at room temperature. The superior performance is ascribed to the inter and intra crosslinking structures of quadruple H-bonding and polyrotaxanes in the dual crosslinking system. Strain-induced crystallization of PEG in polyrotaxanes also contributes to the high fracture energy of the elastomers. Furthermore, based on the dual cross-linked supramolecular elastomer, a highly stretchable and self-healable electrode containing liquid metal is also fabricated, retaining resistance stability (0.16-0.26 Ω) even at the strain of 1600 %.

Dual-hard phase structures make mechanically tough and autonomous self-healable polyurethane elastomers

It is a key challenge to combine high mechanical strength and excellent autonomous self-healing properties in one elastomer to match the requirements of commercial applications. Chemical cross-linking or ordered crystalline domains can afford high mechanical strength but are often based on the cost of losing autonomous self-healing performance. To address this dilemma, a strategy involving dual hard-phase structures was developed to reinforce self-healing polyurethane elastomers, by introducing plant oil-derived aliphatic chains into the hard segments. The dangling fatty acids not only allow segmental motion of the hard domains but also suppress the crystallization within polyurethane soft segments. The tailored dual-hard phase structure and dynamic chain motion are responsible for outstanding mechanical properties (tensile strength to 21.8 MPa and toughness of 131.6 MJ m−3) and autonomous self-healing ability (∼100 % healing efficiency). Furthermore, a versatile mechanical robust flexible conductor is conveniently constructed with an auto-repair capability at ambient conditions. This work represents a molecular design paradigm of simultaneously integrating balanced mechanical strength, durability, and self-healing ability for high-performance elastomers that can find applications such as skin-inspired wearable devices.

Self-Healing and Super-Elastomeric PolyMEA-co-SMA Nanocomposites Crosslinked by Clay Platelets.

Novel solvent-free ultra-extensible, tough, and self-healing nanocomposite elastomers were synthesized. The self-assembled materials were based on the copolymer matrix poly(methoxyethyl acrylate-co-sodium methacrylate) physically crosslinked by clay nano-platelets (‘poly[MEA-co-SMA]/clay’). Depending on the content of SMA, the super-elastomers were predominantly hydrophobic, water-swelling, or fully water-soluble, and hence repeatedly processible. The SMA co-monomer introduces a tremendous increase in tensile strength, an increase in toughness, while ultra-extensibility is preserved. By tuning the contents of nano-clay and SMA co-monomer, a very wide range of product properties was achieved, including extreme ultra-extensibility, or high stiffness combined with more moderate super-extensibility, or very different values of tensile strength. There was very attractive, great improvement in autonomous self-healing ability induced by SMA, combined with tremendously enhanced self-recovery of internal mechanical damage: even complete self-recovery could be achieved. The ionic SMA repeat units were found to assemble to multiplets, which are phase-separated in the hydrophobic polyMEA matrix. The dynamics of SMA-units-hopping between these aggregates was of key importance for the mechanical, visco-elastic, tensile, and self-healing properties. The studied super-elastomers are attractive as advanced self-healing materials in engineering, soft robotics, and in medical or implant applications.

Tough and Degradable Self-Healing Elastomer from Synergistic Soft-Hard Segments Design for Biomechano-Robust Artificial Skin.

Increasing biomechanical applications of skin-inspired devices raise higher requirements for the skin-bionic robustness and environmental compatibility of elastomers. Here, a tough and degradable self-healing elastomer (TDSE) is developed by a synergistic soft-hard segments design. The polyester/polyether copolymer is introduced in soft segments to endow TDSE with flexibility and degradability. The two isomeric diamines are regulated in hard segments for elevating the toughness and fracture energy to 82.38 MJ/m3 and 43299 J/m2 and autonomous self-healing ability with 93% efficiency in 7 h for the TDSE. Employing TDSE and ionic liquid, a biomechano-robust artificial skin (BA-skin) is constructed with a stretch-insensitive mechanosensation capability during 50% cyclic stretching. The BA-skin has high biomechano-robustness to bear tear damage and good environmental compatibility with total decomposability in a lipase solution. This work provides a molecular design guideline for high-performance skin-bionic elastomers for applications in skin-inspired devices.

Highly Stretchable Fully Biomass Autonomic Self-Healing Polyamide Elastomers and Their Foam for Selective Oil Absorption.

Renewable polymers with self-healing ability, excellent elongation, hydrophobicity, and selective oil absorption attributes are of interest for an extensive range of applications, such as e-skin, soft robots, wearable devices, and cleaning up oil spills. Herein, two fully renewable eco-friendly polyamide (PA)-based self-healing elastomers (namely, PA36,IA, and PA36,36) were prepared by a facile and green one-pot melt polycondensation of itaconic acid (IA), PripolTM 1009, and PriamineTM 1075 monomers. The molecular structures of these PAs were analyzed by FITR, 1H NMR, and 13C NMR. The distinct structure of these PAs shows superior strain values (above 2300%) and high ambient temperature autonomous self-healing ability. Interestingly, the synthesized renewable PA36,36 showed zero water absorption values and hydrophobic properties with a contact angle of θ = 91° compared to the synthesized PA36,IA and other previously reported PAs. These excellent attributes are due to the low concentration of amide groups, the highly entangled main chains, the intermolecular diffusion, the manifold dangling chains, and the numerous reversible physical bonds within the renewable PAs. Furthermore, the hydrophobic properties may aid in the selective oil absorption of the PA36,36-based foam, for which PA36,36 foam is produced by the green supercritical carbon dioxide (scCO2) batch foaming process. The PA36,36 foam with a microporous cellular structure showed better absorption capacity and high stability in repeated use. Due to these advantages, these bio-based PAs have potential for the production of eco-friendly self-healing materials, superabsorbent foams, and other polymeric materials.

Autonomous self-healing hydrogel with anti-drying properties and applications in soft robotics

Mimicking nature's self-healing ability has always been desired in science, especially when devices accumulate damage over time with performance, including the loss of function due to deterioration. SHAP (Self-Healing AETA([2-(acryloyloxy)ethyl]trimethylammonium chloride)-based Polymer), a hydrogel with autonomous self-healing ability that can be applied for the development of a pneumatic artificial muscle, is presented here. Unlike other self-healing hydrogels, SHAP does not require any external stimulus to self-heal and it presents outstanding anti-drying properties. Few-layer graphene is also incorporated into the polymer network of the hydrogel in order to study the possible influence that the nanomaterial has on the properties of the scaffolds. The mechanical behavior and the self-healing abilities of the resulting hydrogels are analyzed. Moreover, the mechanism of self-healing is discussed in terms of experimental results and theoretical calculations. The data suggest a mechanism based on strong hydrogen-bonding interactions between the water molecules that remain inside SHAP, which keeps the material wet and soft under ambient conditions. Finally, the development of a SHAP-based artificial muscle is presented. The results show good performance of the healed artificial muscles after damage, even with healing periods as short as 10 minutes.

Highly Stretchable and Conductive Self-Healing Hydrogels for Temperature and Strain Sensing and Chronic Wound Treatment.

Flexible bioelectronics for biomedical applications requires a stretchable, conductive, self-healable, and biocompatible material that can be obtained by cost-effective chemicals and strategies. Herein, we synthesized polypyrrole or Zn-functionalized chitosan molecules, which are cross-linked with poly(vinyl alcohol) to form a hydrogel through dynamic di-diol complexations, hydrogen bonding, and zinc-based coordination bonds. These multiple dynamic interactions endow the material with excellent stretchability and autonomous self-healing ability. The choice of Food and Drug Administration (FDA)-approved materials (poly(vinyl alcohol) and chitosan) as the matrix materials ensures the good biocompatibility of the hydrogel. The conductivity contributed by the polypyrrole allowed the hydrogel to sense strain and temperature, and the coordinated Zn significantly enhanced the antibacterial activity of the hydrogel. Moreover, using a diabetic rat model, we have proved that this hydrogel is capable of promoting the healing of the infected chronic wounds with electrical stimulation.

A dual supramolecular crosslinked polyurethane with superior mechanical properties and autonomous self-healing ability

The dual-dynamic networks endow polyurethane with excellent mechanical properties and autonomous self-healing ability.

Solid-state and liquid-free elastomeric ionic conductors with autonomous self-healing ability

Solid-state and liquid-free self-healing ion-conductive elastomers with high ionic conductivity are developed and exploited as stretchable and pressure-independent touch sensors.

Conductive Self-Healing Nanocomposite Hydrogel Skin Sensors with Antifreezing and Thermoresponsive Properties.

With growing interest in flexible and wearable devices, the demand for nature-inspired soft smart materials, especially intelligent hydrogels with multiple perceptions toward external strain and temperatures to mimic the human skin, is on the rise. However, simultaneous achievement of intelligent hydrogels with skin-compatible performances, including good transparency, appropriate mechanical properties, autonomous self-healing ability, multiple mechanical/thermoresponsiveness, and retaining flexibility at subzero temperatures, is still challenging and thus limits their application as skinlike devices. Here, conductive nanocomposite hydrogels (NC gels) were delicately designed and prepared via gelation of oligo(ethylene glycol) methacrylate (OEGMA)-based monomers in a glycerol-water cosolvent, where inorganic clay served as the physical cross-linker and provided conductive ions. The resultant NC gels exhibited good conductivity (∼3.32 × 10-4 S cm-1, akin to biological muscle tissue) and an autonomously self-healing capacity (healing efficiency reached 84.8%). Additionally, such NC gels displayed excellent flexibility and responded well to multiple strain/temperature external stimuli and subtle human motions in a wide temperature range (from -20 to 45 °C). These distinguished properties would endow such NC gels significant applications in fields of biosensors, human-machine interfaces, and soft robotics.

Ultra-Stretchable Conductive Polymer Complex As a Wearable Strain Sensor with Excellent Linearity and Repeatable Autonomous Self-Healing Ability

Wearable strain sensors are essential for the realization of applications in the broad fields of remote healthcare monitoring, soft robots, immersive gaming, among many others. These flexible sensors should be comfortably adhered to skin and capable of monitoring human motions with high accuracy, as well as exhibiting excellent durability. However, it is challenging to develop electronic materials that possess the properties of skin—compliant, elastic, stretchable, and self-healable. This work demonstrates a new regenerative polymer complex composed of poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAAMPSA), polyaniline (PANI) and phytic acid (PA) as a skin-like electronic material. It exhibits ultrahigh stretchability (1935%), excellent repeatable autonomous self-healing ability (repeating healing efficiency > 98%), and exceptional linearity (R2 > 0.995) — outperforming current reported wearable strain sensors. The deprotonated polyelectrolyte, multivalent anion, and doped conductive polymer, under ambient conditions, synergistically construct a regenerative dynamic network of polymer complex crosslinked by hydrogen bonds and electrostatic interactions, which enables ultrahigh stretchability and repeatable self-healing. Sensitive strain-responsive geometric and piezoresistive mechanisms of the material owing to the homogenous and viscoelastic nature provide excellent linear responses to omnidirectional tensile strain and bending deformations. Furthermore, this material is scalable and simple to process in an environmentally-friendly manner, paving the way for the next generation flexible electronics. Figure 1

Ultrastretchable Conductive Polymer Complex as a Strain Sensor with a Repeatable Autonomous Self-Healing Ability.

Wearable strain sensors are essential for the realization of applications in the broad fields of remote healthcare monitoring, soft robots, and immersive gaming, among many others. These flexible sensors should be comfortably adhered to the skin and capable of monitoring human motions with high accuracy, as well as exhibiting excellent durability. However, it is challenging to develop electronic materials that possess the properties of skin-compliant, elastic, stretchable, and self-healable. This work demonstrates a new regenerative polymer complex composed of poly(2-acrylamido-2-methyl-1-propanesulfonic acid), polyaniline, and phytic acid as a skin-like electronic material. It exhibits ultrahigh stretchability (1935%), repeatable autonomous self-healing ability (repeating healing efficiency >98%), quadratic response to strain ( R2 > 0.9998), and linear response to flexion bending ( R2 > 0.9994), outperforming current reported wearable strain sensors. The deprotonated polyelectrolyte, multivalent anion, and doped conductive polymer, under ambient conditions, synergistically construct a regenerative dynamic network of polymer complex cross-linked by hydrogen bonds and electrostatic interactions, which enables ultrahigh stretchability and repeatable self-healing. Sensitive strain-responsive geometric and piezoresistive mechanisms of the material owing to the homogeneous and viscoelastic nature provide excellent linear responses to omnidirectional tensile strain and bending deformations. Furthermore, this material is scalable and simple to process in an environmentally friendly manner, paving the way for the next-generation flexible electronics.

A highly stretchable, self-healing, recyclable and interfacial adhesion gel: Preparation, characterization and applications

Gels with excellent performance, especially self-healing ability have attracted much attention on account of their potential use. However, it is necessary to study many issues, such as the preparation of gels, self-healing mechanism and their application. In this paper, we developed a facile and reliable strategy to fabricate poly(vinyl alcohol) (PVA)/phytic acid (PA) gel. Compared with pure PVA gel, PVA/PA gel not only possesses high stretchability (>1000%), but also combines efficient autonomous self-healing ability. PVA/PA gel could autonomously self-heal swiftly based on hydrogen bonding at room temperature without any external stimuli, even it is left alone for a long time. PVA/PA gel also presents excellent recyclability which can be recycled by hot pressing. Furthermore, it possesses good interfacial adhesion to various materials that can benefit for preparation of electronic device. Meanwhile, because PVA can be used as the electrolyte, self-healing capacitor can be prepared with superior performance based on the PVA/PA gel. In brief, because of the superior performance, PVA/PA gel can be used as a promising candidate in many fields such as electrodes, supercapacitors, batteries, particularly in the fabrication of next-generation wearable and portable electronics.

Facile and cost-effective synthesis of glycogen-based conductive hydrogels with extremely flexible, excellent self-healing and tunable mechanical properties

In materials science and engineering, the designing of hydrogels with excellent self-healing and tunable mechanical properties is an inviting issue. In this study, we introduce the sacrificial bonds interactions in a hybrid hydrogel of natural and synthetic polymers, to give a hydrogel with autonomous self-healing ability and tunable mechanical properties. Glycogen, a natural polymer tends to strengthen the hydrogel while PVA, a synthetic polymer plays a critical role in the flexibility and stretchability of the hydrogel. Hydrogels were designed by the sacrificial non-covalent interactions with physical cross-linking of the polymer chains to the trivalent metal ions. Functional groups of the polymers interact with sacrificial hydrogen bonds with and with the metal ions, they interact through sacrificial coordination interactions with different strength, results tunable sacrificial bonds. Weaker sacrificial bonds rupture prior to the strong sacrificial bonds upon external loading, which dissipate the energy and endow the hydrogel with adjustable mechanical and self-healing properties. The tunable mechanical properties and excellent self-healing efficiency enlarge the application areas of the developed hydrogel in various fields.

Polymers with autonomous self-healing ability and remarkable reprocessability under ambient humidity conditions

A strategy of utilizing atmospheric moisture for self-healing polymers is investigated.

A Transparent, Highly Stretchable, Autonomous Self-Healing Poly(dimethyl siloxane) Elastomer.

An innovative self-healing polydimethylsiloxane (PDMS) elastomer, namely, PDMS-TFB, is reported by incorporating the reversibly dynamic imine bond as the self-healing points into the PDMS networks. The PDMS-TFB elastomer features good optical transmittance (80%) in full visible light region, high stretchability (≈700%), and excellent autonomous self-healing ability at room temperature. Surprisingly, the self-healing behavior can take place in water and even at a temperature as low as -20 °C in air, showing a promising outlook for broader applications. As a proof-of-concept, this study demonstrates the use of the PDMS-TFB elastomer for preparing anticorrosion coating and adhesive layer, and also the use of such an elastomer to be the platform for fabricating the flexible interconnector and chemical sensor. Remarkably, no significant difference is observed between the pristine and healed samples. Taking full advantage of these unique properties, it is anticipated that such a PDMS-TFB elastomer shows wide applications in the fields of materials science, electronics, biology, optics, etc.

Self-Assembly-Directed Aerogel and Membrane Formation from a Magnetic Composite: An Approach to Developing Multifunctional Materials.

Herein, we report the preparation of an aerogel and a membrane from a magnetic composite material by tuning the self-assembly at the molecular level. The gel exhibits an excellent oil absorption property, and the membrane shows a remarkable autonomous self-healing property. The composite is formed from an organosilicon-modified poly(amidoamine) (PAMAM) dendrimer, which is linked with iron oxide nanoparticles and poly(vinyl alcohol). Upon the addition of a cross-linker (formaldehyde), the system undergoes a fast self-assembly and gelation process. The aerogel, obtained after drying of the hydrogel, was modified with 1- bromohexadecane at room temperature and utilized for the removal of oil from water with 22.9 g/g absorption capacity. Intriguingly, the same system forms a membrane with 97% autonomous self-healing ability, in the absence of the cross-linker. The membrane was used to remove the salt content from water with an efficiency of 85%. The control experiments suggest that the presence of the magnetic material (iron oxide) plays a key role in the formation of both the aerogel and membrane.