Search Results (48)

Hydrogel sensors show unique advantages in underwater detection, ocean monitoring, and human–computer interaction because of their excellent flexibility, biocompatibility, high sensitivity, and environmental adaptability. However, due to the water environment, hydrogels will dissolve to a certain extent, resulting in insufficient mechanical strength, poor long-term stability, and signal interference. In this paper, a double-network structure was constructed by polyvinyl alcohol (PVA) and poly([2-(methacryloyloxy) ethyl]7 dimethyl-(3-sulfopropyl) ammonium hydroxide) (PSBMA). The resultant PVA/PSBMA-PA hydrogel demonstrated notable swelling resistance, a property attributable to the incorporation of non-covalent interactions (electrostatic interactions and hydrogen bonding) through the addition of phytic acid (PA). The hydrogel exhibited high stretchability (maximum tensile strength up to 304 kPa), high conductivity (5.8 mS/cm), and anti-swelling (only 1.8% swelling occurred after 14 days of immersion in artificial seawater). Assembled as a sensor, it exhibited high strain sensitivity (0.77), a low detection limit (1%), and stable electrical properties after multiple tensile cycles. The utilization of PVA/PSBMA-PA hydrogel as a wearable sensor shows promise for detecting human joint movements, including those of the fingers, wrists, elbows, and knees. Due to the excellent resistance to swelling, the PVA/PSBMA-PA-based sensors are also suitable for underwater applications, enabling the detection of underwater mannequin motion. This study proposes an uncomplicated and pragmatic methodology for producing hydrogel sensors suitable for use within subaquatic environments, thereby concomitantly broadening the scope of applications for wearable electronic devices. Full article

Polyimine-based composites have emerged as a promising class of dynamic covalent thermosets, combining high mechanical strength, thermal stability, self-healing, recyclability, and reprocessability. This review systematically summarizes recent advances in polyimine synthesis, highlighting dynamic covalent chemistry (DCC) strategies such as imine exchange and reversible Schiff base reactions. Structural customization can be achieved by incorporating reinforcing phases such as carbon nanotubes, graphene, and bio-based fibers. Advanced fabrication methods—including solution casting, hot pressing, and interfacial polymerization—enable precise integration of these components while preserving structural integrity and adaptability. Mechanical performance analysis emphasizes the interplay between dynamic bonds, interfacial engineering, and multiscale design strategies. Polyimine composites exhibit outstanding performance characteristics, including a self-healing efficiency exceeding 90%, a tensile strength reaching 96.2 MPa, and remarkable chemical recyclability. Emerging engineering applications encompass sustainable green materials, flexible electronics, energy storage devices, and flame-retardant systems. Key challenges include balancing multifunctionality, enhancing large-scale processability, and developing low-energy recycling strategies. Future efforts should focus on interfacial optimization and network adaptivity to accelerate the industrial translation of polyimine composites, advancing next-generation sustainable materials. Full article

Furan/maleimide dynamic covalent chemistry has been extensively used to fabricate re-workable and self-healing thermosets. Understanding the relationship between crosslinker structure, network dynamics, and material final properties, however, remains a challenge. This study introduces self-healing and shape-memory thermosets derived from furan-functionalized polyketones (PKFU) crosslinked with aromatic bis-maleimides, i.e., 1,1′-(methylenedi-4,1-phenylene)bis-maleimide (BISM1) and bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (BISM2), via a thermally reversible Diels-Alder reaction. Polyketones were chemically modified with furfurylamine through the Paal-Knorr reaction, achieving varying furan grafting ratios. The resulting networks, characterized by ATR-FTIR, ¹H-NMR, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and rheology, demonstrated tunable thermomechanical properties. BISM2-based thermosets exhibited enhanced thermal stability and reversibility over a broad temperature range (20–120 °C), with a shape recovery ratio of up to 89% and complete self-healing at 120 °C within 5 min. These findings highlight the potential of polyketone-based thermosets for applications requiring adaptive thermomechanical properties, efficient self-repair, and sustainability. Full article

Self-healing composites are designed based on natural healing processes such as bone regeneration and blood coagulation. These composites have polymeric material containing covalent adaptable networks that rearrange their molecular structure when heated, thereby serving as a healing agent. The inclusion of the healing polymers into the principal matrix of the fiber-reinforced composites alters their off-axis properties. In addition, the healing agents tend to bleed out of the composite structures upon heating. It is, therefore, essential to characterize the extent of the changes in the off-axis properties of the self-healing composites. In this research work, three different configurations of self-healing composites are subjected to three-point bending tests, and their healing characteristics are studied using Acousto-Ultrasonic tests. Frequencies of the propagating stress waves in the AU tests are used to analyze the different conditions of the self-healing composites, such as virgin, damaged, damaged-partially healed, and damaged-fully healed. The results show that the AU test could potentially be used to evaluate the healing behavior of these fiber-reinforced self-healable composites. Full article

To fulfill the current circular economy concept, the academic and industrial communities are devoting significant efforts to plastic materials’ end-of-life. Unlike thermoplastics, which are easy to recover and re-valorize, recycling thermosets is still difficult and challenging. Conversely, because of their network structure, thermosetting polymer systems exhibit peculiar features that make these materials preferable for several applications where high mechanical properties, chemical inertness, and thermal stability, among others, are demanded. In this view, vitrimers have quite recently attracted the attention of the scientific community, as they can form dynamic covalent adaptive networks that provide the properties typical of thermosets while keeping the possibility of being processed (and, therefore, mechanically recycled) beyond a certain temperature. This review aims to provide an overview of vitrimers, elucidating their most recent advances and applications and posing some perspectives for the forthcoming years. Full article

Carbon-fiber-reinforced polymers (CFRPs) with epoxy matrices are widely applied in high-performance structural applications and represent one of the biggest classes of materials with urgent need for end-of-life management. Available waste management methodologies for conventional thermoset composites with a focus on CFRPs are briefly reviewed and their limitations are highlighted. In the quest to obtain materials with mechanical performance, thermal stability, and sustainability, the research community has turned its interest to develop polymer composites with adaptable and dynamic networks in their matrix, and lately also at an interface/interphase level. The current review focuses on the life extension/waste management options that are opened through the introduction of covalent adaptable networks in the epoxy matrix of CFRPs. The processing conditions that are applied for the healing/repairing, welding/reshaping, and/or recycling of CFRPs are presented in detail, and compared based on the most common dynamic exchange reactions. Full article

This study’s integration of molecular dynamics (MD) simulations with non-covalent adaptable networks (NANs) and corroborative wet lab experiments offers a comprehensive approach to understanding the interactions between ritonavir (RTV) and polymers in supersaturated solutions. This multifaceted study not only explored the stabilization mechanisms facilitated by NANs but also examined the influence of polymer selection on the pharmaceutical properties of RTV, a class III compound known for its slow crystallization rate. This research utilized molecular dynamics simulations to model the intermolecular interactions between RTV and two polymers, Polyvinylpyrrolidone (PVP) K30 and Eudragit L100. These simulations were specifically designed to incorporate the effects of NANs, highlighting their dynamic nature and potential to enhance drug stability and solubility. Simultaneously, wet lab experiments were conducted to measure the nucleation induction times and observe the crystallization behavior of RTV under varying conditions of polymer presence. The experimental data demonstrated a significant extension in nucleation induction time, prolonging the duration from 12 to approximately 64 h when PVP K30 and Eudragit L100 were present. This substantial delay in crystallization was attributed to the strong intermolecular interactions between RTV and the polymers, which were effectively stabilized by the non-covalent bonds within the NANs. These findings were consistently confirmed across both computational and experimental settings, illustrating how NANs can effectively inhibit crystallization and enhance the supersaturation state of RTV. This study successfully demonstrates how the physical and chemical properties of polymers influence the crystallization process of poorly water-soluble drugs such as RTV. Leveraging the synergy between computational simulations and empirical laboratory data, this research provides deep insights into the mechanisms at play, ensuring that drug formulations are optimized for both stability and performance. Full article

Covalent adaptable networks (CANs) are polymer networks cross-linked via dynamic covalent bonds that can proceed with bond exchange reactions upon applying external stimuli. In this report, a series of cross-linked polyacrylate films were fabricated by changing the combination of acrylate monomer and the amount of diacrylate cross-linker possessing oxime–urethane bonds as a kind of dynamic covalent bond to evaluate their rheological relaxation properties. Model analysis of the experimental relaxation curves of cross-linked polyacrylate films was conducted by assuming that they consist of two types of relaxation, one of which is related to the oxime–urethane bond exchange reaction, and another of which is associated with the melting of the aggregated cross-linker. It was found that the contribution from the relaxation due to the bond exchange reaction becomes dominant only when the normal-alkyl acrylates are used as a monomer. The relaxation time was almost constant even when the amount of the cross-linker was adjusted. Moreover, it was also indicated that the miscibility of the cross-linker is very important for the fabrication of CANs with good self-healing ability and reprocessability. Full article

A covalent adaptable network (CAN) of semicrystalline polyolefin blends with triple-shape memory effects was fabricated by the reactive melt blending of maleated polypropylene (mPP) and maleated polyolefin elastomer (mPOE) (50 wt/50 wt) in the presence of a small amount of a tetrafunctional thiol (PETMP) and 1,5,7-triazabicyclo [4,4,0]dec-5-ene (TBD). The polymer blend formed a chemically crosslinked network via the reaction between the thiol group of PETMP and maleic anhydride of both polymers in the blend, which was confirmed by FTIR, the variation of torque during the melt mixing process, a solubility test, and DMA. DSC analysis revealed that the crosslinked polyolefin blends show two distinct crystalline melting transitions corresponding to each component polymer. Improved tensile strength as well as elongation at break were observed in the crosslinked blend as compared to the simple blend, and the mechanical properties were maintained after repeated melt processing. These results suggest that thermoplastic polyolefin blends can be transformed into a high-performance and value-added material with good recyclability and reprocessability. Full article

Until recently, recycling thermoset polyurethanes (PUs) was limited to degrading methods. The development of covalent adaptable networks (CANs), to which PUs can be assigned, has opened novel possibilities for actual recycling. Most efforts in this area have been directed toward inventing new materials that can benefit from CAN theory; presently, little or nothing has been applied to industrially producible materials. In this study, both an industrially available polyol (Sovermol780^®) and isocyanate (Tolonate X FLO 100^®) with percentages of bioderived components were employed, resulting in a potentially scalable and industrially producible material. The resultant network could be reworked up to three times, maintaining the crosslinked structure without significantly changing the thermal properties. Improvements in mechanical parameters were observed when comparing the pristine material to the material exposed to three rework processes, with gains of roughly 50% in elongation at break and 20% in tensile strength despite a 25% decrease in Young’s modulus and crosslink density. Thus, it was demonstrated that theory may be profitably applied even to materials that are not designed including additional bonds but instead rely just on the dynamic urethane bond that is naturally present in the network. Full article

Covalent adaptable networks and vitrimers are novel polymers with dynamic reversible bond exchange reactions for crosslinks, enabling them to modulate their properties between those of thermoplastics and thermosets. They have been gathering interest as materials for their recycling and self-healing properties. In this review, we discuss different molecular simulation efforts that have been used over the last decade to investigate and understand the nanoscale and molecular behaviors of covalent adaptable networks and vitrimers. In particular, molecular dynamics, Monte Carlo, and a hybrid of molecular dynamics and Monte Carlo approaches have been used to model the dynamic bond exchange reaction, which is the main mechanism of interest since it controls both the mechanical and rheological behaviors. The molecular simulation techniques presented yield sufficient results to investigate the structure and dynamics as well as the mechanical and rheological responses of such dynamic networks. The benefits of each method have been highlighted. The use of other tools such as theoretical models and machine learning has been included. We noticed, amongst the most prominent results, that stress relaxes as the bond exchange reaction happens, and that at temperatures higher than the glass transition temperature, the self-healing properties are better since more bond BERs are observed. The lifetime of dynamic covalent crosslinks follows, at moderate to high temperatures, an Arrhenius-like temperature dependence. We note the modeling of certain properties like the melt viscosity with glass transition temperature and the topology freezing transition temperature according to a behavior ruled by either the Williams–Landel–Ferry equation or the Arrhenius equation. Discrepancies between the behavior in dissociative and associative covalent adaptable networks are discussed. We conclude by stating which material parameters and atomistic factors, at the nanoscale, have not yet been taken into account and are lacking in the current literature. Full article

Economic and environmental concerns over the accumulation of end-of-life carbon fibre composite waste have led to increased attention to sustainable materials with low environmental impact. Over decades of research, vitrimers, a modern class of covalent adaptable networks, have bridged the gap between thermoplastics and thermosets. With the distinguishing feature of dynamic covalent bonds, vitrimers can be rearranged and reprocessed within their existing network structures in response to external stimuli such as heat or light. This poses a unique solution to repairing damaged composites, extending their service life, and reducing post-consumer waste. However, the synthesis of vitrimers often requires petrochemical consumption, which increases their carbon footprint. Using bio-based materials could be a promising solution to reduce the reliance on petrochemicals and their related pollution. This review compiles the contemporary requirements for bio-based vitrimers regarding their properties, scalability, and recycling features. This article also presents a comprehensive overview of the pathways to produce sustainable bio-based vitrimers and an overview of promising studies showing the potential uses of bio-derived vitrimers on carbon fibre composite productions. Full article

The Diels–Alder equilibrium is a widely known process in chemistry that can be used to provide a thermoset structure with recyclability and reprocessability mechanisms. In this study, a commercial epoxy resin is modified through the integration of functional groups into the network structure to provide superior performance. The present study has demonstrated that it is possible to adapt the curing process to efficiently incorporate these moieties in the final structure of commercial epoxy-based resins. It also evaluates the impact that they have on the final properties of the cured composites. In addition, different approaches have been studied for the incorporation of the functional group, adjusting and adapting the stoichiometry of the system components due to the differences in reactivity caused by the presence of the incorporated reactive groups, with the objective of maintaining comparable ratios of epoxy/amine groups in the formulation. Finally, it has been demonstrated that although the Diels–Alder equilibrium responds under external conditions, such as temperature, different sets of parameters and behaviors are to be expected as the structures are integrated into the thermoset, generating new equilibrium temperatures. In this way, the present research has explored sustainable strategies to enable the recyclability of commercial thermoset systems through crosslinking control and its modification. Full article

This paper developed a method for preparing ultrasound-responsive microgels based on reversible addition fragmentation chain transfer-hetero Diels–Alder (RAFT-HAD) dynamic covalent bonding. First, a styrene cross-linked network was successfully prepared by a Diels–Alder (DA) reaction between phosphoryl dithioester and furan using double-ended diethoxyphosphoryl dithiocarbonate (BDEPDF) for RAFT reagent-mediated styrene (St) polymerization, with a double-ended dienophile linker and copolymer of furfuryl methacrylate (FMA) and St as the dienophile. Subsequently, the microgel system was constructed by the HDA reaction between phosphoryl disulfide and furan groups using the copolymer of polyethylene glycol monomethyl ether acrylate (OEGMA) and FMA as the dienophore building block and hydrophilic segment and the polystyrene pro-dienophile linker as the cross-linker and hydrophobic segment. The number of furans in the dienophile chain and the length of the dienophile linker were regulated by RAFT polymerization to investigate the effects of the single-molecule chain functional group degree, furan/dithioester ratio, and hydrophobic cross-linker length on the microgel system. The prepared microgels can achieve the reversible transformation of materials under force responsiveness, and their preparation steps are simple and adaptive to various potential applications in biomedical materials and adaptive electrical materials. Full article

Thermosets have been crucial in modern engineering for decades, finding applications in various industries. Welding cross-linked components are essential in the processing of thermosets for repairing damaged areas or fabricating complex structures. However, the inherent insolubility and infusibility of thermoset materials, attributed to their three-dimensional network structure, pose challenges to welding development. Incorporating dynamic chemical bonds into highly cross-linked networks bridges the gap between thermosets and thermoplastics presenting a promising avenue for innovative welding techniques. External stimuli, including thermal, light, solvent, pH, electric, and magnetic fields, induce dynamic bonds’ breakage and reformation, rendering the cross-linked network malleable. This plasticity facilitates the seamless linkage of two parts to an integral whole, attracting significant attention for potential applications in soft actuators, smart devices, solid batteries, and more. This review provides a comprehensive overview of dynamic bonds employed in welding dynamic cross-linked networks (DCNs). It extensively discusses the classification and fabrication of common epoxy DCNs and acrylate DCNs. Notably, recent advancements in welding processes based on DCNs under external stimuli are detailed, focusing on the welding dynamics among covalent adaptable networks (CANs). Full article