Self-healing Polymers Research Articles

Polyhydroxyalkanoates: Medical Applications and Potential for Use in Dentistry

Polyhydroxyalkanoates (PHAs) are promising biopolymers as an alternative to traditional synthetic polymers due to their biodegradability and biocompatibility. The PHA market is blooming in response to the growing demand for biodegradable and environmentally friendly plastics. These biopolyesters are produced and degraded by a variety of microorganisms, making them environmentally friendly, while offering benefits such as biocompatibility (when adequately processed) and biodegradability. Their versatility extends to various areas, from biomedicine to agriculture and composite materials, where they pave the way for significative innovations. In the field of regenerative medicine, some PHAs have key applications, namely in vascular grafts, oral tissue regeneration, and development of self-healing polymers. In addition, PHAs have the potential to be used in the creation of dental implant materials and dental medical devices. PHAs can also be used to encapsulate hydrophobic drugs, providing an approach for more targeted and effective treatments. To summarize, PHAs open new perspectives in the field of medicine by improving drug delivery and offering ecologically biocompatible solutions for medical devices. The aim of this review is to present the medical and dental applications of PHA, their advantages, disadvantages, and indications.

Integrating Photothermal-Responsive Shape Memory and Self-Healing Polymers in 4D-Printed Thermally Comfortable Smart Wearables

Integrating Photothermal-Responsive Shape Memory and Self-Healing Polymers in 4D-Printed Thermally Comfortable Smart Wearables

Strong self-healing close-loop recyclable vitrimers via complementary dynamic covalent/non-covalent bonding

Epoxy vitrimers represent a new class of high-performance sustainable resins because of their desired mechanical and thermally malleable properties. Unfortunately, existing epoxy vitrimers cannot self-heal at room temperature (R.T.) due to the trade-off between mechanical robustness, recyclability, and the ‘frozen’ state of vitrimer networks at R.T. Herein, a high-performance hyperbranched epoxy vitrimer (DCNC/50PEDA) via curing bis(2,3-epoxypropyl) cyclohex-4-ene-1,2-dicarboxylate (DCNC) with 50 wt% of a phosphorus/silicon-containing polyethyleneimine (PEDA) at R.T., and the key to this design lies in rationally integrating complementary dynamic non-covalent hydrogen-bonding and π-π stacking and covalent β-hydroxy ester bonds into the high-mobility branched units of the DCNC/50PEDA network. This design endows the vitrimer with a room-temperature self-healing efficiency up to 96.0 %, high mechanical strength reaching 36.0 MPa, and desired closed-loop recyclability. Moreover, its strong adhesion to a variety of substrates and exceptional fire retardancy, e.g., a limiting oxygen index of 39.0 % and a desired UL-94 V-0 rating, make it an outstanding fire-retardant coating for flammable substrates, such as wood. Such a performance portfolio enables DCNC/50PEDA to outperform existing self-healing polymer and vitrimers counterparts. This work establishes a promising complementary dynamic design protocol for creating self-healing, strong, recyclable, and fire-safe polymers by integrating dynamic non-covalent interactions and covalent bonds, which hold great real-world applications in industries, such as bulk materials, coatings, and adhesives.

MXene-reinforced water insensitive self-healing piezoelectric nanogenerator for ambient and aquatic mechano-pressure sensing

The development of soft electronic devices capable of autonomous self-healing (SH) holds immense potential across various endeavours, promising to revolutionize product durability, reliability, and maintenance practices. Despite some progress has been made, underwater stable SH continues to be an active area of research. Herein, SH polymer PDMS-MDI0.4-TFB0.6 (SHP) with excellent mechanical property was composited with MXene to investigate the piezoelectric nature under various circumstance. By leveraging MXene into SHP not only improves the material properties of mechanical stress but also permittivity of the elastomer. Thus, MXene incorporated SHP (mSHP) induce high polarized charges under mechanical pressure. The fabrication of mSHP piezoelectric nanogenerator (mSHP-PENG) device via spray coating AgNWs on the surface forms ohmic contact, which facilitate high sensitivity and flexibility. Nevertheless, the generated piezoelectricity (30 V, 4.2 μA: 3 Hz) upon mechanical pressure gives maximum power density of 128 μW/m2 indicating that our device can act as a reliable power source for portable electronic gadgets. In addition, SHP with amphiphilic functional groups sustain the original shape even after immerse into water for so long. Taking this into account, our device undergoes effective deformation even at low pressures, thus render to fabricate touch sensitive piezo-switches for both atmospheric and aquatics environments.

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.

In Situ Alloying Enabled by Active Liquid Metal Filler for Self-Healing Composite Polymer Electrolytes.

Solid inorganics, known for kinetically inhibiting polymer crystallization and enhancing ionic conductivity, have attracted significant attention in solid polymer electrolytes. However, current composite polymer electrolytes (CPEs) are still facing challenges in Li metal batteries, falling short of inhibiting severe dendritic growth and resulting in very limited cycling life. This study introduces Ga62.5In21.5Sn16 (Galinstan) liquid metal (LM) as an active liquid alternative to conventional passive solid fillers, aiming at realizing self-healing protection against dendrite problems. Compared to solid inorganics, for example silica, LM droplets could more significantly reduce polymer crystallinity and enhance Li-ion conductivity due to their liquid nature, especially at temperatures below the polymer melting point. More importantly, LMs are unraveled as dynamic chemical traps, which are capable of blocking and consuming lithium dendrites upon contact via in situ alloying during battery operation and further inhibiting dendritic growth due to the lower deposition energy barrier of the formed Li-LM alloy. As a proof of concept, by strategically designing an asymmetric CPE with the active LM filling, a solid-state Li/LiFePO4 battery achieves promising full-cell functionality with notable rate performance and stable cycle life. This active filler-mediated self-healing approach could bring new insights into the battery design in versatile solid-state systems.

Ultra-Tough, yet Rigid and Healable Supramolecular Polymers with Variable Stiffness for Multimodal Actuators.

Variable stiffness materials have shown considerable application in soft robotics. However, previously reported materials often struggle to reconcile high stiffness, stretchability, toughness, and self-healing ability, because of the inherently conflicting requisite of these properties in molecular design. Herein, we propose a novel strategy that involves incorporating acid-base ionic pairs capable of from strong crosslinking sites into a dense and robust hydrogen-bonding network to construct rigid self-healing polymers with tunable stiffness and excellent toughness. To demonstrate these distinct features, the polymer was employed to serve as the strain-regulation layers within a fiber-reinforced pneumatic actuator (FPA). The exceptional synergy between the configuration versatility of FPA and the dynamic molecular behavior of the supramolecular polymers equips the actuator with simultaneous improvement in motion dexterity, multimodality, loading capacity, robustness, and durability. Additionally, the concept of integrating high dexterity at both macro- and micro-scale is prospective to inspire the design of intelligent yet robust devices across various domains.

A Novel Super-Toughness and Self-Healing Solid Polymer Electrolyte for Solid Sodium Metal Batteries.

Solid sodium metal batteries (SSMBs) offer an alternative promising power source for electrochemical energy storage due to their high energy density and high safety. However, the inherent sodium dendrite growth and poor mechanical properties of electrolytes seriously limit their application. Herein, a network structure composed of polyethylene oxide-based composite polymer electrolyte (CPE) is designed with liquid metal nanoparticles (LM) for SSMBs, in which LM can move in the solid electrolyte with the electric field driven. This effect can facilitate the inactivated sodium return to the metal sodium anode, and alloy with dendrites at the same time, which is beneficial for inhibiting the growth of dendrites. The symmetric cell with the CPE containing LM achieves good cyclic stability of more than 1800 and 800h at 0.1 and 0.2mAcm-2, respectively. The energy density of the pouch battery can reach 230Whkg-1. In sum, LM presents great potential to be employed as a performance reinforcement filler for CPEs, which paves the way for achieving high-performance SSMBs.

Polyetherimide copolymer film with room-temperature self-healing properties and high breakdown field strength

With the waste of resources caused by human activities, it has gradually become an increasingly prominent social problem. The development of self-healing polymers in the field of insulation has attracted widespread attention. Develop polymer matrices with efficient healing efficiency and sound insulation properties to achieve green and sustainable resource conservation. In addition, improving the dielectric properties of intrinsic self-healing matrices has been a hot topic. In this work, we developed a new PEI matrix-modified self-healing polymer substrate that provides a breakdown field strength of 240 kV/mm and self-healing properties at room temperature, this has significantly improved the dielectric properties over other previously reported self-healing polymers. In addition to the abovementioned performance, we found significant differences in thermodynamic behavior in the synthesized end-modified polymers. By dielectric characterization (LCR), the breakdown composite can be left at room temperature for 60 min, and the material can recover 80 % of the initial properties without external intervention(This is demonstrated by the fact that its DC conductivity at 60 min of autonomous healing was significantly changed from that of the freshly electrically pierced DC conductivity and remained around 5.38 × 10−11 S/cm for a longer period of time thereafter). The microscopic morphology of the modified PEI matrix was observed by scanning electron microscopy (SEM) and EDS surface elemental analysis, which further supports the existence of metal coordination structures. These findings can further deepen the thinking of self-healing dielectric composites. The work inspired by this may break the limits and take self-healing composite dielectric materials to a new height.

Alkaline-Responsive, Self-Healable, and Conductive Copolymer Composites with Enhanced Mechanical Properties Tailored for Wearable Tech.

Despite significant advancements, current self-healing materials often suffer from a compromise between mechanical robustness and functional performance, particularly in terms of conductivity and responsiveness to environmental stimuli. Addressing this issue, the research introduces a self-healable and conductive copolymer, poly(ionic liquid-co-acrylic acid) (PIL-co-PAA), synthesized through free radical polymerization, and further optimized by incorporating thermoplastic polyurethane (TPU). This combination leverages the unique properties of each component, especially ion-dipole interactions and hydrogen bonds, resulting in a material that exhibits exceptional self-healing abilities and demonstrates enhanced mechanical properties and electrical conductivity. Moreover, the PIL-co-PAA/TPU films showcase alkaline-responsive behavior, a feature that broadens their applicability in dynamic environments. Through systematic characterization, including thermogravimetric analysis, tensile testing, and electrical properties measurements, the mechanisms behind the improved performance and functionality of these films are elucidated. The conductivities and ultimate tensile strength (σuts) of the PIL-co-PAA/TPU films regain 80% under 8h healing process. To extend the applications for wearable devices, the self-healing properties of commercial cotton fabrics coated with the self-healable PIL-co-PAA are also investigated, demonstrating both self-healing and electrical properties. This study advances the understanding of self-healable conductive polymers and opens new avenues for their application in wearable technology.

Self-healing Hydrophobic Antifouling Polymers with Fe3+-Catechol Coordination Interaction.

Hydrophobic antifouling polymers capable of self-healing performance are highly desirable for industrial applications. However, the construction of self-healing, hydrophobic antifouling polymers is challenging considering their complex fouling environments, which are humid in aqueous environment. In this work, a self-healing hydrophobic polymer containing Fe3+-catechol coordination applicable to antifouling is synthesized. The hydrophobic fluoroalkyl segments in the polymers formed unique domains dispersed in a polydimethylsiloxane matrix. The as-synthesized polymers can completely restore their tensile strength, and their self-healing efficiency is above 90% in both artificial seawater and pure water because of the dynamic Fe3+-catechol coordination interactions. The as-synthesized polymer exhibited self-healing and antifouling properties against common marine bacteria. The colony adhesion and self-healing processes of the damaged coating in artificial seawater containing marine bacteria are characterized by laser confocal microscopy. This strategy may be useful for the development of future polymeric antifouling materials.

Fast thermo-responsive thermoset self-healing polymers based on bio-derived Benzoxazine/Epoxidized castor oil copolymers for coating applications

This work emphasized on development of a novel bio-derived self-healing copolymer fabricated from benzoxazine and epoxy resins by varying weight ratios. The bio-derived benzoxazine (E-fa) acted as a healing agent was copolymerized with bio-derived epoxy resin namely epoxidized castor oil (ECO). Three main essential properties of the developed copolymer were systematically investigated: thermal property, mechanical property, and self-healing capacity. The numerical simulation was also used to study and predict the ability of roof coatings based on the developed copolymers. The results showed that the reversible crosslinking reaction occurred and resulted in state transition of the copolymers. The mechanical property i.e., tensile strength and peel strength to stainless steel substrate, were substantially improved with the incorporation of ECO. The increase in E-fa contents can enhance the thermos-responsive healing performance of the copolymers up to 93% via reversible reactions with rapid surface damage healed within 2 min. Furthermore, the experimental and numerical results revealed that the thermo-responsive thermoset self-healing bio-derived benzoxazine/epoxy copolymers have a potential use in coating applications required fast self-healing performance and good mechanical properties.

Ferroelastic ionic organic crystals that self-heal to 95%

The realm of self-healing materials integrates chemical and physical mechanisms that prevent wear and fracturing and extend the operational lifetime. Unlike the favorable rheology of amorphous soft materials that facilitates efficient contact between fragments, the efficiency of recovery of atomistically ordered materials is restricted by slower interfacial mass transport and the need for ideal physical alignment, which limits their real-world application. We report drastic enhancements in efficiency and recovery time in the self-healing of anilinium bromide, challenging these limitations. Crystals of this material recovered up to 49% within seconds and up to 95% after 100 min via ferroelastic detwinning. The spatial evolution of strain during cracking and healing was measured in real time using digital image correlation. Favorable alignment and strong ionic bonding across the interface of partially fractured crystals facilitate self-healing. This study elevates organic crystals close to the best-in-class self-healing polymers and sets an approach for durable crystal-based optoelectronics.

Multiscale study on fatigue healing performance and molecular healing behavior of self-healing SBS modified bitumen

Self-healing polymer modified bitumen based on dynamic chemical bonds is a potential approach to improve the durability of bitumen pavement and save fossil energy. Herein, a novel self-healing SBS modified bitumen on the basis of dynamic disulfide bonds and hydrogen bonds was prepared. Firstly, an aliphatic disulfide (A-ALD) with disulfide bonds and hydrogen bonds was synthesized. Then A-ALD/SBS modified bitumen (A-ALD/SMB) was prepared by blending A-ALD and SBS modified bitumen. The chemical structure and microstructure of A-ALD/SMB were evaluated. In addition, the self-healing performance of A-ALD/SMB at the macroscopic scale and the self-healing behavior at the molecular scale were investigated by a combination of fatigue healing test and molecular dynamics (MD) simulation. The chemical structure analysis showed the formation of disulfide bonds and hydrogen bonds in A-ALD, and A-ALD was successfully attached to the CC bonds in SBS. Fluorescent images revealed that a better network structure appeared in A-ALD/SMB and formed a two-phase continuous morphology. The optimal dosage of A-ALD in SBS modified bitumen was 0.6 %. The fatigue healing test results indicated that A-ALD markedly enhanced the self-healing ability of SBS modified bitumen, and prolonging resting time and raising healing temperature can increase the self-healing performance of A-ALD/SMB. When the damage degree, healing temperature, and resting time were 30 %, 30 °C, and 60 min, respectively, the healing rate of A-ALD/SMB was 98.5 %, which was 30.2 % higher than SMB. The MD simulation results showed that the A-ALD enhanced the molecular diffusion capacity of SBS modified bitumen, and crack healing time of A-ALD/SMB was earlier than that of SMB under the same conditions. When the healing temperature was 40 °C, the time for the A-ALD/SMB and SMB molecular chain segments to start contacting and healing was 27 ps and 49 ps, respectively, which was improved by 44.9 % for A-ALD/SMB compared to SMB. Furthermore, the self-healing behavior of A-ALD/SMB at the molecular scale was consistent with the self-healing performance at the macroscopic scale under different healing temperatures and damage degrees. This study provided a theoretical basis for exploring the self-healing mechanism of SBS modified bitumen.

Room-temperature self-healing polyurethane with superior mechanical properties based on supramolecular structure for flame retardant application

Self-healing polymers, with their ability to extend service life and conserve resources, have garnered significant attention across various fields due to their immense potential applications. However, most repairable polymers typically require high temperatures for repair, and their relatively weak mechanical properties limit their practical use. Moreover, the flammability of polymers not only poses safety hazards during use but also fails to meet specific requirements for flame retardancy in certain fields. Addressing these issues, this study successfully designed a reactive self-extinguishing room-temperature self-healing polyurethane (PU) by introducing hyperbranched catechol (DBPA) onto the PU main chain. The prepared self-healing PU elastomer (DPU) exhibited high tensile strength (∼51.2 MPa), outstanding toughness (∼119.0 MJ/m3), recyclability, and good flame retardancy. Through intermolecular and intramolecular multilevel hydrogen bonding, the prepared DPU0.6 achieved room-temperature self-healing with an efficiency of approximately 71.2 %. The results showed that the addition of trace amounts of DBPA (0.6 wt%) significantly enhanced the flame retardancy and thermal stability of DPU. Compared to DPU0, the heat release rate (HRR) of DPU0.6 decreased by approximately 13 %, the total heat release (THR) reduced by 18 %, and the time to ignition (TTI) was extended by 7 s (reduced by ∼ 21 %). This study not only provides insights into the synthesis and design of novel self-healing PU but also further expands the application scope of self-healing PU.

Supramolecular Association of a Block Copolymer via Strong Hydrogen Bonding to Form Self-Healable Ionogels.

The drive to enhance the operational durability and reliability of stretchable and wearable electronic and electrochemical devices has led to the exploration of self-healing materials that can recover from both physical and functional failures. In the present study, we fabricated a self-healable solid polymer electrolyte, referred to as an ionogel, using reversible hydrogen bonding between the ureidopyrimidone units of a block copolymer (BCP) network swollen in an ionic liquid (IL). The BCP consisted of poly(styrene-b-(methyl acrylate-r-ureidopyrimidone methacrylate)) [poly(S-b-(MA-r-UPyMA)], with the IL-phobic polystyrene forming micellar cores that were interconnected via intercorona hydrogen bonding between the ureidopyrimidone units. By precisely regulating the molecular weight and the composition of the hydrogen-bondable motifs, the mechanical, electrical, and self-healing characteristics of the ionogel were systematically evaluated. The resulting ionogel samples exhibited suitable stretchability, ionic conductivity, and room-temperature self-healability due to reversible hydrogen bonding. To highlight the applicability of the self-healing ionogel as a high-capacitance gate insulator, an electrolyte-gated transistor (EGT) was fabricated using a poly(3-hexylthiophene-2,5-diyl) semiconductor, and the performance of the EGT was fully recovered from a complete cut without any external stimuli.

Recent advancements in self-healing materials and their application in coating industry

Self-healing polymers (SHP), inspired by nature, are materials that have the ability to recover themselves from various physical damages in the presence of different inducing environments. The self-recovering property indicates the capability to heal the cracks in their very nascent stage at their micro or nano-level size and provides a door to prevent them from any major catastrophic failure. In this article, a comprehensive review with updated reported work on various types of self-healing mechanisms and their advantages and limitations has been discussed, along with their applications. The main focus of the review has been aligned with the challenges and future scopes associated with the exploration of self-healing concepts for industrial coating applications. The different extrinsic, intrinsic, and combined healing mechanisms have been explained, along with their application in coating. Finally, the recent status of healing technology and future research trends has been discussed in this review article.

Multiphase hydrogen bonding strategies room temperature self-healing, recyclable polyurethane elastomers for applications in flame retardant materials

Novel elastomers offer new opportunities to develop multifunctional materials in terms of combining mechanical strength, room-temperature self-healing properties and recyclability. However, self-healing polymers have high mechanical strength at high internal cross-linking density, but restrict the movement of molecular chain segments leading to reduced self-healing efficiency. The presence of microphase-separated structures makes the polymers poorly efficient for repair at room temperature. In this paper, a multiphase hydrogen bonding (H-bonding) strategy is used to introduce an aliphatic ring into the system to form a repeating unit with the hard segments, as well as a bis-benzene ring structure with a methylene linkage to disrupt the crystallization of the hard domains. Specifically, PUPI-M2I3 has a mechanical tensile strength of 17.93 MPa, an excellent tensile ratio of 1109.88 %, the sample can recover 95.93 % at room temperature after 24 h of fracture and stretching, with excellent room temperature self-healing performance and recyclability. Meanwhile, the self-healing flame-retardant material based on PUPI-M2I3 is developed by comprehensive consideration, which opens a new way for the research and development of flame-retardant materials.

Evaluation of self-repair efficiency of polymers containing microcapsules using optical coherence tomography

Self-healing polymers are used to improve the durability and strength of materials and provide them with a longer service life. The authors propose a new optical method for evaluating the self-repair efficiency in polymers containing microcapsules. The non-destructive method measures spatial profiles of a hole series obtained after a material puncture. Spatial images of holes acquired by optical coherence tomography were processed to get a surface profile. The reduction of the average volume or depth of the holes compared to the reference material allows self-healing efficiency calculation. For the presented method, tests were carried out to measure the self-repair efficiency of test materials with 5% and 10% mass of repair capsules compared to Ethe reference polymer without capsules. The volumetric efficiencies of self-repair obtained from 30 holes of each material, acquired 8 h after the puncture, were computed as 51.6% and 58.3% for the two repaired material types, respectively.

Additive manufacturing of Diels-Alder self-healing polymers: Separate heating system to enhance mechanical, healing properties and assembly-free smart structures

Over the past decades, self-healing polymers have become increasingly popular due to their unique ability to recover mechanical and functional properties after sustaining structural damage, which significantly extends their lifespan compared to traditional polymers. Material Extrusion (MEX) 3D printing has recently emerged as a possible manufacturing approach for processing self-healing polymers; however, commercial MEX 3D printers lack of the flexibility to fabricate complex and functional structures based on such materials. In this work, an innovative MEX setup for extruding self-healing polymer networks based on a thermo-reversible reaction is presented. The proposed approach is based on the leverage of a separate heating system (SHS), enabling the degelation of the self-healing polymer network into a printable ink. This SHS regulates both the syringe-barrel, and nozzle temperatures during the processing (degelation and extrusion) of self-healing inks, leading to enhanced mechanical performance (Young modulus, tensile strength), and extrusion accuracy of 3D printed structures. The effectiveness of the SHS-based approach is demonstrated by an improved geometrical accuracy (filament deviation reduced by 26 %), which is directly correlated to the mitigation of the extrusion force (variability reduced by 77 %). Moreover, the SHS approach also improved both the mechanical properties and the self-healing performance of the printed parts. Finally, two different self-healing polymers a dielectric and an electrically conductive were extruded in a single manufacturing cycle to fabricate a self-sensing structure. This structure is capable of detecting bending with a sensitivity of 3.10 Ω/degree, even after healing. This paper aims to advance the role of MEX beyond its current limitations by enabling processing of high-quality self-healing structures with embedded sensors.