Self-healing Materials Research Articles

Liquid metal-enhanced MoS2 nanocomposite for self-healing colloidal anodes in lithium-ion batteries

Energy storage is pivotal in addressing global energy challenges, with lithium-ion batteries (LIBs) at the forefront. However, their longevity is often limited by anode material degradation. Here, we introduce a novel LM/AgNWs@MoS2 nanocomposite anode material, synthesized via a one-step hydrothermal method, which integrates liquid metal's fluidity with silver nanowires' conductivity and MoS2's rapid lithium-ion diffusion. This composite demonstrates exceptional cycling stability, maintaining 468 mA h g−1 over 2000 cycles at 1 A g−1, and self-heals electrode cracks, offering a significant advancement for LIBs durability and safety. The LM/AgNWs@MoS2 nanocomposite addresses the critical need for durable, self-healing anode materials in LIBs, pushing forward the development of next-generation energy storage solutions.

Enhancing the Self-Healing Efficiency of Ti3AlC2 MAX Phase via Irradiation.

Self-healing materials are highly desirable in the nuclear industry to ensure nuclear security. Although extensive efforts have been devoted to developing self-healing materials in the past half century, very limited successes have been reported for ceramics or metals. Here, we report an intrinsic self-healing material of Ti3AlC2 MAX phase, which exhibits both ceramic and metallic properties, and a strategy for further enhancing the self-healing via irradiation is proposed. Quantitative in situ transmission electron microscopy tensile testing reveals that the fracture strength of 1.58 GPa is achieved on thoroughly fractured Ti3AlC2, corresponding to the self-healing efficiency of 19.8%, which is increased to 28.1% after irradiation. In situ irradiation experiments, atomic-resolution characterizations, and molecular dynamics simulations reveal that spontaneous rebonding of partial atoms on fracture surfaces is responsible for the self-healing, and irradiation-enhanced atomic migration, interplanar spacing increment, and gap-filling contribute to the self-healing enhancement.

Stereochemical Shape Morphing in Diels-Alder Polymer Networks.

The intrinsic reversibility of dynamic covalent bonding, such as the furan-maleimide Diels-Alder (DA) cycloaddition reactions, enables reprocessable, self-healing polymer materials that can be reconfigured via the mechanism of solid-state plasticity. In this work, the temperature-dependent exchange rates of stereochemically distinct endo and exo DA bonds are leveraged to achieve tunable, temperature- and stress-activated shape morphing in Diels-Alder polymer (DAP) networks. Through thermal annealing, ≈35% of endo DA isomers are converted in neat DAP networks to the thermodynamically favored exo form, achieving ≈97% exo after complete annealing at 60°C. This conversion results in a ≈1.7 fold increase in elastic modulus, from 1.7 to 3.0MPa, and significantly alters the stress relaxation and shape recovery behavior. Spatially resolved annealing, is further showcased enabling the precise control of spatial distributions of endo and exo DA bonds across planar geometries. The locally distinct concentrations of endo/exo isomers, achieved by temperature-induced conversion of endo DA isomers to the thermodynamically stable exo DA isomers, gave rise to the spatial distributions of stress relaxation rates and elastic strain recovery mismatch to enable controlled stereochemical shape morphing. This approach provides a simplified, thermally driven method for shape morphing, with potential applications in soft robotics and flexible electronics.

Facile Preparation and Study of Self-Healing Water-Absorbing Expanding Elastomers.

The absorbent expansion elastomer plays a crucial role in engineering sealing and holds a promising future in this field as infrastructure continues to develop. Traditional materials have their limitations, especially when used in large construction projects where the integrity and reliability of the material are of utmost importance. In this work, a self-healing water-absorbing expansion elastomer was developed for continuous production at a large scale to monitor the sealing conditions of massive infrastructure projects. At room temperature, the material exhibited a repairing efficiency of 57.77 % within 2 h, which increased to 84.02 % after 12 h. This extended reaction time allowed for effective repairs when defects were detected. The material's strength can attain 3 MPa, placing it at the upper echelon among common self-healing materials, thereby granting it a certain level of durability in its application environment. The material's volume expansion rate reached 200-400 % to achieve effective sealing, and the functional filling of the filler endowed the material itself with a favorable external force induction effect and prevented heat accumulation. The conductive detection performance of the absorbent expansion elastomer was improved by utilizing triple self-healing strategies, including dipole-dipole interaction, ion cross-linked network, and externally-aided restoration materials. These strategies were combined with a double packing strategy to enhance the material's properties. This innovative elastomer can be applied in various fields such as tunnel construction, infrastructure development, aerospace sealing, and railway transportation, showcasing significant potential for diverse engineering applications.

Unveiling the Impact of Absorbent Polymers on Self-healing Efficiency of Sludge-derived Capsules in Cementitious Composites

A novel green capsule for self-healing cementitious material using a combination of waste-based materials with an inorganic substance was developed. A mix of alum sludge (AS), a typical waste from the water industry, and calcium hydroxide were used as the primary healing agents. Also, two types of natural and synthetic absorbent polymers (AP), microcrystalline cellulose (MCC) and sodium polyacrylate (SPA), were added to the core mixture to assess their impact on the healing efficiency. The morphology of the produced capsules, the self-healing proficiency of cracked mortars, and the resulting healing materials were characterised. Outcomes revealed that cracks up to 400µm could be healed by the plain capsule. The closure width was dramatically increased to 500µm and 800µm with the inclusion of MCC and SPA, respectively, mainly in 3 days. The expansion, water retention, and bridging properties of the APs enhanced the sealing performance of the capsules by providing nucleation sites and increasing the reaction rates of core materials to generate further calcium-based products inside the cracks. Therefore, higher recovery rates of mechanical strengths, along with a significant reduction in water ingress were achieved. The main healing products were identified as calcite crystals, C-S-H, calcium silicate, and aluminium-bearing phases.

Novel hybrid coating material with triple distinct healing bond for fat oil and grease deposition control in the sewer system

Hybrid materials with distinct self-healing bonds are a prominent category of materials, demanding in various modern applications. Developing self-healable hybrid materials with desired self-healing properties at ambient conditions is highly desirable and challenging. Herein, we developed a novel zinc (II)–dimethylglyoxime–urethane-complex-based polyurethane elastomer (Zn-polyurethane hybrid material) with synergetic triple dynamic bonds, which exhibits spontaneous self-healing properties at 30 °C. Moreover, this material shows excellent thermal stability up to approximately 850 °C and is highly stable in water systems. This hybrid material has potential applications in water systems; in this study, we characterized it for fat, oil and grease (FOG) deposition management in sewer systems by applying it as a coating on concrete blocks. The findings indicate that following a 30-day leaching test conducted under controlled pH conditions on uncoated and Zn-polyurethane-coated concrete blocks, a reduction of over 80 % in calcium release was observed in the coated block compared to the uncoated concrete block. Additionally, in FOG deposit formation tests conducted on uncoated and coated concrete blocks for 30 days, a reduction of over 30 % in FOG deposit formation was noted in the coated sample.

Research on the properties of crystalline admixtures: Self-healing healing materials for concrete from multiple perspectives

The research on the self-healing of concrete promoted by crystal admixtures provides a new direction for the green development of construction industry. In this study, three crystal admixtures, i.e., l-aspartic acid (LAA), Na2SiO3 and nano-silica (NS), were screened from the experimental results in terms of promotion of hydration, fast reaction, and effective filling. The three components were mixed as concrete self-healing agents, and the experimental ratio was designed by response surface method. Finally, the optimal ratio was selected according to the visual healing effect. The durability of mortar with the optimum ratio of self-healing agent was studied by the experiment of resistance to chloride ion and sulfate attack; its preliminary heat release was studied by hydration microcalorimeter. The microscopic analysis was carried out by X-ray powder diffraction (XRD), thermogravimetric analysis (TG), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) test and mercury injection method (MIP). The experimental results showed that the best healing effect was achieved when the dosage of LAA, Na2SiO3 and NS reached 0.5 %, 0.4 % and 0.15 % of the cement mass. In the process of healing, the early healing products are mainly calcium carbonate, and the late healing products are mainly ettringite and calcium silicate hydrate (CSH), and the healing agent effectively reduces the porosity and improves the pore structure, making the concrete matrix more dense.

Mechanically robust, self-healing and stretchable electromagnetic shielding materials based on multi-component dynamic bonded polyurethane elastomer

Stretchable self-healing electromagnetic interference (EMI) shielding materials can automatically restore their original performance after mechanical damage, and can still maintain over 20 dB EMI shielding effectiveness (EMI SE) under tensile state. In this work, a series of highly stretchable self-healing polyurethane elastomer PUBNS-X was prepared by introducing dynamic disulfide bonds, boronic ester bonds and boron-nitrogen coordination (B-N) on the polyurethane main chain. It was found that B-N coordination significantly increased the elongation at break and the tensile strength. The high dynamic reversibility of boronic ester, disulfide bond and B-N coordination bond synergistically endowed PUBNS-X with excellent temperature-triggered self-healing properties. The mechanical properties of PUBNS-X can be restored to more than 90 % at 60 °C. The pre-assembled silver nanowires (AgNWs) conductive network was then introduced into the polyurethane surface by taking advantage of the fluidity of the dynamically bonded polyurethane backbone to obtain a series of stretchable self-healing electromagnetic shielding composites (AgNWs/PUBNS-Y). The results showed that the EMI SE of AgNWs/PUBNS-Y can reach ∼55 dB, and the conductivity can be restored to 82 % of the original value after healing at 60 °C. The investigation of the electromagnetic interference shielding performance of composites under different strains showed that the EMI SE of AgNWs/PUBNS-3 can still maintain 20 dB under 90 % strain. These composites will have broad potential applications in the fields of flexible wearable electronic products, bionic intelligent materials and soft robots.

Self-healing and wave-absorbing functional coupling of nano-Fe3O4 hybridized microcapsules

As a common high-performance wave absorber, the application prospect of nano-Fe3O4 in cementitious materials is limited due to its defects such as easy agglomeration and possible hydration reaction with cement clinker. In this study, self-healing and wave-absorbing functional coupling materials were synthesized by nano-Fe3O4 hybridized microcapsules. The physical and chemical properties of nano-Fe3O4 hybridized microcapsules were characterized by ESEM (Environmental scanning electron microscopy), XRD (X-ray diffractometer) and FTIR (Fourier transform infrared spectrum), etc. The self-healing properties of microcapsules were assessed. The electromagnetic parameters of microcapsules were measured, and the wave-absorbing performance of microcapsules with different matching thicknesses was assessed. The function coupling mechanism of self-healing and wave-absorbing of microcapsules hybridized by nano-Fe3O4 was revealed. The findings revealed that the residual weights of FM0 and FM40 were 1.28 % and 16.44 %, respectively. The hybrid microcapsules demonstrated the amorphous structure of self-healing microcapsules and the crystal structure characteristics of nano-Fe3O4. The highest strength healing rate of cement mortar mixed with microcapsules was 34.2 %. The minimum reflection loss and the corresponding effective bandwidth of the nano-Fe3O4 hybridized microcapsules with a thickness of 3 mm were −20.32 dB and 7.07 GHz, respectively. The nano-Fe3O4 hybridized microcapsules with core–shell structure exhibit excellent wave-absorbing performance through the functional coupling of dielectric loss and magnetic loss.

An innovative sludge-derived capsule for self-healing cementitious materials

An innovative eco-efficient capsule utilizing drinking water treatment sludge (DWTS) as a healing agent for concrete crack sealing was developed. In this study, the core materials comprised a mix of DWTS and calcium hydroxide, granulated by poly (ethylene glycol). A non-toxic polymer, Ethyl cellulose (EC), is applied as the protective shell material. The morphology, internal structure, and leakage mechanism of capsules, self-healing performance of cracked mortars and the composition of resulting healing products were assessed. Obtained results indicated that EC uniformly covered the spherical core material following the designed coating procedures. The main elements released from the capsules were Ca, Al and Si after dissolution of polyethylene glycol (PEG), which would contribute to pozzolanic reactions inside the matrix. Cracks with an initial width of 400 μm were completely healed after 7 days of curing. Such a healing process also led to an 73% enhancement in compressive strength at a healing age of 28 days. The water tightness of capsule-based samples improved by more than 90% in the first 7 days, compared to only 10% in control samples. The predominant healing products were calcium carbonate in the form of calcite, and some content of aluminium-bearing phases derived from the pozzolanic reaction of DWTS.

3D Printing with Self-Healing Materials and Applications

3D printing also called as the additive manufacturing. It is revolutionizing various industries by enabling the production of complex objects directly from digital models. This technology offers significant advantages over traditional manufacturing methods. Especially in reducing material waste and increased design flexibility. The range of 3D printing application contains healthcare to aerospace, reflecting its growing importance in modern society. Recently, 3D printing advancements have introduced in self-healing (SH) materials, it saved limitations related to the durability and repairability of printed objects. SH materials are categorized into external and internal systems. External SH materials use embedded healing agents that repair damage through chemical reactions, while internal systems rely on dynamic bonding within the material itself. This innovation not only extends the functional life of 3D printed items but also supports trends in mass customization and sustainability. This paper explores the mechanisms, types, and applications of SH materials in 3D printing, and mainly focus on their potential to enhance product longevity and functionality across medical, construction, and consumer goods sectors.

Effects of Isocyanate Structure on the Properties of Polyurethane: Synthesis, Performance, and Self-Healing Characteristics.

Polyurethane (PU) plays a critical role in elastomers, adhesives, and self-healing materials. We selected the most commonly used aromatic isocyanates, 4,4'-methylene diphenyl diisocyanate (MDI) and tolylene-2,4-diisocyanate (TDI), and the most commonly used aliphatic isocyanates, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and dicyclohexylmethane-4,4'-diisocyanate (HMDI), as raw materials, combined with polytetramethylene ether glycol (PTMG) and 1,4-butanediol (BDO) to successfully synthesize five PU materials. The effects of isocyanate structure on polymerization rate, hydrogen bonding, thermal properties, phase separation, wettability, self-healing performance, adhesion, and mechanical properties were systematically investigated. The results show that isocyanates with higher symmetry facilitate hydrogen bonding, but excessive flexibility and crystallinity may inhibit its formation. MDI-based PU exhibits the highest hydrogen bonding index (HBI) of 4.10, along with the most distinct phase separation and the highest tensile strength of 23.4 MPa. HMDI-based PU demonstrates the best adhesion properties, with the highest lap shear strength of 7.9 MPa, and also exhibits excellent scratch healing ability. IPDI-based PU shows good self-healing performance, recovering 88.7% of its original tensile strength and 90.6% of its original lap shear strength after heating at 80 °C for 24 h. Furthermore, all the samples can be reprocessed by melt or solution methods, showing excellent recyclability.

Research Progress of Human Biomimetic Self-Healing Materials.

Humans can heal themselves after injury, which inspires researchers to develop bionic self-healing materials. Such materials not only equipped with the self-repair capacities akin to those of the human body, but also emulate the mechanical properties of human organs, including the tensile resilience of muscles, the fatigue resistance of skin, and the elevated modulus typical of cartilage. Based on the design concept of imitating the structure of human organs, the bionic self-healing material perfectly solves the problem of poor mechanical properties of self-healing materials caused by weak bond energy and inter-chain flow. This review discusses various organ-inspired self-healing materials in detail, summarizes their synthetic principles and introduces their fascinating mechanical properties. Finally, the application prospects of bionic self-healing polymer materials, such as bio-strain sensors, self-healing anticorrosive coatings, biomedical detection, etc., are outlined. Considering the excellent comprehensive performance and multi-functions of human biomimetic self-healing polymers, more outstanding sustainable materials will be developed, accelerating research progress in self-healing materials and realizing environmentally friendly products in multiple fields.

A Versatile Microporous Design toward Toughened yet Softened Self-Healing Materials.

Realizing the full potential of self-healing materials in stretchable electronics necessitates not only low modulus to enable high adaptivity, but also high toughness to resist crack propagation. However, existing toughening strategies for soft self-healing materials have only modestly improves mechanical dissipation near the crack tip (ГD), and invariably compromise the material's inherent softness and autonomous healing capabilities. Here, a synthetic microporous architecture is demonstrated that unprecedently toughens and softens self-healing materials without impacting their intrinsic self-healing kinetics. This microporous structure spreads energy dissipation across the entire material through a bran-new dissipative mode of adaptable crack movement (ГA), which substantially increases the fracture toughness by 31.6 times, from 3.19 to 100.86 kJ m-2, and the fractocohesive length by 20.7 times, from 0.59 mm to 12.24 mm. This combination of unprecedented fracture toughness (100.86 kJ m-2) and centimeter-scale fractocohesive length (1.23 cm) surpasses all previous records for synthetic soft self-healing materials and even exceeds those of light alloys. Coupled with significantly enhanced softness (0.43 MPa) and nearly perfect autonomous self-healing efficiency (≈100%), this robust material is ideal for constructing durable kirigami electronics for wearable devices.

Fiber-Reinforced Flexible Self-Healing Strain Sensor with Failure-Improving Sensitivity Recovery.

In this work, we address the inherent limitations of porous, flexible, fibrous, and self-healing strain sensors. Specifically, we tackle issues such as the fatigue failure of carbon-fibrous materials and the long-term flow and low mechanical stability of self-healing materials. We achieve this by combining self-healing carbon/PBS blends with fibrous materials, creating a fiber-reinforced self-healing composite. The self-healing carbon/PBS blends provide strain sensitivity and the ability to recover after fatigue and impact failure, while the fibers prevent the long-term flow of material and the scattering of pieces during impact and fatigue failure within the elastic deformation regime, enabling shape recovery. We fabricated composite wearable strain sensors with a viscoelastic functional layer composed of two continuous phases: (i) a self-healing polymer-carbon blend and (ii) long electrospun fibers of commercial polyurethane. This setup also eliminates the other drawbacks of bulk materials, such as nonlinearity of volt-ampere characteristics, irreversibility of deformation, and a low working factor, and allows improvement of the working factor after failure and healing. Most importantly, we discovered that hindered self-healing, like in the case of the MWCNT/PBS system, enables improvement of sensor sensitivity after large strains and failure, which is due to partial failure of the network formed by conductive particles.

Robust self-healing capacity and high mechanical properties of castor oil-based waterborne polyurethane based on “kill two birds with one stone” strategy

Achieving ideal combination of high self-healing efficiency and good mechanical properties is of significance for the breakthrough in the application of self-healing materials. Herein, the functionalized castor oil-based waterborne polyurethane (DA-CWPU) was constructed based on “killing two birds with one stone” molecular design strategy with the addition of self-healing monomer D-A adduct. Firstly, D-A adduct containing flexible D-A bonds and rigid ring structure was prepared by D-A reaction with furfuryl alcohol (FA) and bismaleimide (BMI) as raw materials, which could not only effectively enhanced the self-healing ability of the material, but also ensured the strong mechanical properties. Then, DA-CWPU emulsion with favourable self-healing and mechanical properties was synthesized by the polymerization of castor oil (CO), isophorone diisocyanate (IPDI) and D-A adduct. The DA-CWPU film has preferable self-healing efficiency (93 % at 100 °C for 50 min), unique shape memory effect (rehabilitate after heating at 100 °C for 45 s), good toughness (485 MJ/m3), strong tensile strength (5.96 MPa) and sufficient elongation (115 %). At the same time, the self-healing DA-CWPU film can be recycled through solution casting. The sustainable castor oil-based waterborne polyurethane can be used as finishing agents for leather products, which realizes repeatedly self-healing in case of surface damage, greatly increasing the service life of the material and mechanical properties, providing a new approach for the development of mechanically robust self-healing materials.

Advanced Vitrimer with Spiropyran Beads: A Multi-Responsive, Shape Memory, Self-Healing, and Reprocessable Smart Material.

Thermosetting materials have limitations in terms of reshaping and recycling due to their irreversible bond structures, leading to significant plastic waste issues. Recently, epoxy vitrimers based on dynamic covalent bond exchange have been introduced as promising alternatives to traditional thermosets. Particularly, they demonstrate significant potential applications in the field of multi-responsive materials. In this research, a self-healable and mechano-responsive vitrimer (EB-V) is successfully prepared, incorporating epoxide spiropyran beads (ESP beads) derived from citric acid and epoxy derivatives. To enable self-reporting of cracks through color changes, ESP beads are covalently bonded to the vitrimer via an epoxy-carboxylic acid reaction. The photochromic properties of EB-V are demonstrated by color and fluorescence changes, and its tensile strength increased from 2.0 to 6.8MPa compared to the control sample. Dynamic mechanical analysis confirmed the covalent exchange reaction of the vitrimer, revealing its reconfigurable behavior and stress relaxation at elevated temperatures. Furthermore, EB-V exhibited exceptional properties, including self-healing and reprocessability. As a smart material, it holds great promise for a wide range of applications, such as sensors, actuators, 4D printing, and industrial safety diagnostics.

Long-term performance and environmental reliability of selfhealing materials in structural applications

The self-healing capabilities of materials have justifiably emerged as the new promising innovation in structural engineering, having the capability of autonomously repairing damages and thus extending the lifetime of a structure. The paper reviews the existing literature on the long-term performance and environmental reliability of various self-healing materials with regard to application in structure-oriented contexts such as concrete, polymers, and composites. In this paper, the mechanisms that are key to microcapsule-based, vascular, and intrinsic self-healing will be analyzed with regard to their effectiveness with time and different environmental conditions. Challenges and limitations are discussed together with recommendations for future research and practical applications.

A Group-Enriched Viscoelastic Model for High-Damping Vitrimers with Many Dangling Chains.

Classical viscoelastic models usually only consider the motion of chain segments and the motion of the entire molecular chain; therefore, they will cause inevitable errors when modeling self-healing vitrimer materials with many group movements. In this paper, a group-enriched viscoelastic model is proposed for self-healing vitrimers where the group effect cannot be neglected. We synthesize a specific damping vitrimer with many dangling chains, surpassing the limited loss modulus of conventional engineering materials. Due to the dangling chains, the damping capability can be improved and the group effect cannot be neglected in the synthesized damping vitrimer. The group-enriched viscoelastic model accurately captures the experimental damping behavior of the synthesized damping vitrimer. Our results indicate that the group-enriched viscoelastic model can improve the accuracy of classical viscoelastic models. It is shown that the group effect can be ignored at low frequencies since the chain segments have sufficient time for extensive realignment; however, the group effect can become significant in the case of high frequency or low temperature.

Self-Powered Tactile Sensors Embedded with Self-Healing Electrodes for Multifunctional Applications.

Tactile-based sensing technology represents one of the most promising methods for interacting with their surrounding environment. Consequently, flexible tactile sensing has garnered significant attention from researchers worldwide. In this study, triboelectricity and piezoelectricity were combined to propose a multifunctional self-powered tactile sensor (MSPTS). Notably, new and innovative self-healing electrodes were embedded and synthesized from HPDMS (poly(dimethylsiloxane)) and boric acid in the MSPTS, MSPTS demonstrated a linear detection range of 0.25-5 kPa with a sensitivity of 246.28 mV/kPa, indicating substantial improvements in sensor sensitivity, output performance, and anti-interference capability. Our method of forming hydrogen bonds between a self-healing material (SHM) and a liquid metal (LM) effectively addressed the issue of LM leakage within the flexible matrix under pressure, thus preventing sensor failure. The borate dynamic bonding conferred self-healing properties to the electrode when it was damaged. The MSPTS was successfully applied to pressure detection, material identification, and human body movement detection, significantly broadening the application range of flexible electronic devices.