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Fatigue performance and self-repairing activity of asphalt binders are two properties that highly influence the fatigue cracking response of asphalt pavement. There are still numerous gaps in knowledge to fill linked with these two characteristics. For instance, current parameters fail to accommodate these two bitumen phenomena fully. This study aims to propose a new procedure to address this issue utilizing the linear amplitude sweep (LAS) test, LAS with rest period (RP) (LASH) test, and simplified viscoelastic continuum damage (S-VECD) model. This research work used four different types of asphalt binders: neat asphalt (NA), self-healing thermoplastic polyurethane (STPU)-modified bitumen (STPB), self-healing poly (dimethyl siloxane) crosslinked with urea bond (IPA1w)-modified bitumen (IPAB), and styrene–butadiene–styrene (SBS)-modified bitumen (SBSB). Before the testing process, all the materials were subjected to short-term and long-term aging. The new procedure showed a superior capacity to analyze and accommodate all bitumen fatigue performances and self-repairing activities compared to the current method. Another finding proved that asphalt binders with a higher self-restoration behavior failed to show a better fatigue performance. Moreover, the higher fatigue performance increments produced by STPU and IPA1w in NA concerning the control bitumen were 123.7% and 143.7%, respectively. Those values were obtained with 1.0% STPU and 0.5% IPA1w in NA. A breakthrough finding demonstrated that asphalt binder fatigue response is augmented when the RP was applied at a higher damage intensity (S) value. STPB and IPAB reached their highest increments of fatigue response, containing 1.0% of STPU and 0.5% of IPA1w, respectively. Those augmentations were 207.54% and 232.64%, respectively. [ABSTRACT FROM AUTHOR]

Despite being primarily categorized as non-autonomous self-healing polymers, we demonstrate the ability of Diels–Alder polymers to heal macroscopic damages at room temperature, resulting in complete restoration of their mechanical properties within a few hours. Moreover, we observe immediate partial recovery, occurring mere minutes after reuniting the fractured surfaces. This fast room-temperature healing is accomplished by employing an off-stoichiometric maleimide-to-furan ratio in the polymer network. Through an extensive investigation of seven Diels–Alder polymers, the influence of crosslink density on self-healing, thermal, and (thermo-)mechanical performance was thoroughly examined. Crosslink density variations were achieved by adjusting the molecular weight of the monomers or utilizing the off-stoichiometric maleimide-to-furan ratio. Quasistatic tensile testing, dynamic mechanical analysis, dynamic rheometry, differential scanning calorimetry, and thermogravimetric analysis were employed to evaluate the individual effects of these parameters on material performance. While lowering the crosslink density in the polymer network via decreasing the off-stoichiometric ratio demonstrated the greatest acceleration of healing, it also led to a slight decrease in (dynamic) mechanical performance. On the other hand, reducing crosslink density using longer monomers resulted in faster healing, albeit to a lesser extent, while maintaining the (dynamic) mechanical performance. [ABSTRACT FROM AUTHOR]

A series of UV-curable urethane (meth)acrylates were obtained by copolymerization of the Diels–Alder adduct (HODA), isophorone diisocyanate, PEG1000, and various hydroxy (meth)acrylates. The aim of the present work was to determine the influence of the chemical structure of the introduced (meth)acrylic groups, i.e., hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate, on the UV-curing process and self-healing properties of cured coatings. The chemical structure of prepolymers was characterized by FTIR and NMR spectroscopy, whereas the UV-curing process was monitored in real time using FTIR and photo-DSC. In turn, the self-healing properties were characterized in relation to the thermally reversible mechanism, which was tested using the following methods: an FTIR spectroscope equipped with a heating attachment; DSC and TG apparatus; and an optical microscope equipped with a stage with programmable heating. The result of comprehensive research on the self-healing of photocurable coatings in the context of the presence of various photoreactive groups and the course of the curing process allows one to control the self-healing process by reducing the effective healing temperature. The self-healing properties, taken together with the fast UV curing of the coatings and excellent properties of cured coatings, make the material attractive for a variety of applications, in particular in cases where coatings are not repaired, e.g., for economic reasons or when it is not possible, such as in flexible electronic screens, car paint film, and aircraft interior finishes. [ABSTRACT FROM AUTHOR]

This review is devoted to the description of methods for the self-healing of polymers, polymer composites, and coatings. The self-healing of damages that occur during the operation of the corresponding structures makes it possible to extend the service life of the latter, and in this case, the problem of saving non-renewable resources is simultaneously solved. Two strategies are considered: (a) creating reversible crosslinks in the thermoplastic and (b) introducing a healing agent into cracks. Bond exchange reactions in network polymers (a) proceed as a dissociative process, in which crosslinks are split into their constituent reactive fragments with subsequent regeneration, or as an associative process, the limiting stage of which is the interaction of the reactive end group and the crosslink. The latter process is implemented in vitrimers. Strategy (b) is associated with the use of containers (hollow glass fibers, capsules, microvessels) that burst under the action of a crack. Particular attention is paid to self-healing processes in metallopolymer systems. [ABSTRACT FROM AUTHOR]

The aim to achieve sustainable development goals (SDG) and cut CO2-emission is forcing researchers to develop bio-based materials over conventional polymers. Since most of the established bio-based polymeric materials demonstrate prominent sustainability, however, performance, cost, and durability limit their utilization in real-time applications. Additionally, a sustainable circular bioeconomy (CE) ensures SDGs deliver material production, where it ceases the linear approach from production to waste. Simultaneously, sustainable circular bio-economy promoted materials should exhibit the prominent properties to involve and substitute conventional materials. These interceptions can be resolved through state-of-the-art bio-vitrimeric materials that display durability/mechanical properties such as thermosets and processability/malleability such as thermoplastics. This article emphasizes the current need for vitrimers based on bio-derived chemicals; as well as to summarize the developed bio-based vitrimers (including reprocessing, recycling and self-healing properties) and their requirements for a sustainable circular economy in future prospects. [ABSTRACT FROM AUTHOR]

Self-healing polymers such as poly(ethylene-co-methacrylic acid) ionomers (PEMAA) can heal themselves immediately after a projectile puncture which in turn lowers environmental pollution from replacement. In this study, the thermal-mechanical properties and self-healing response of a library of 15 PEMAA copolymers were studied to understand the effects of the ionic content (Li, Na, Zn, Mg) and neutralization percentage (13 to 78%) on the results. Differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and tensile testing were used to study the thermo-mechanical properties of PEMAA copolymers while the self-healing response was studied using the projectile test. Puncture sites were observed using scanning electron microscopy (SEM) and the healing efficiency was quantitatively measured using the water leakage test. Five different self-healing responses were observed and correlated to ionic content and neutralization. At high neutralization, divalent neutralizing ions (Zn and Mg) that have stronger ionic interactions exhibited brittle responses during projectile testing. PEMAA samples neutralized with Mg and Li at low concentrations had a higher healing efficiency than PEMAA samples neutralized with Zn and Na at low neutralization. The PEMAA copolymers with higher tensile stress and two distinct peaks in the graph of loss factor versus temperature that indicate the presence of sufficient ionic aggregate clusters had improved healing efficiency. By increasing the neutralization percentage from 20% to 70%, the tensile strength and modulus of the samples increased and their self-healability generally increased. Among the investigated samples, the copolymer with ~50% neutralization by Li salt showed the highest healing efficiency (100%). Overall, the strength and elastic response required for successful self-healing responses in PEMAA copolymers are shown to be governed by the choice of ion and the amount of neutralization. [ABSTRACT FROM AUTHOR]

In this study, the effect of the addition of multi-walled carbon nanotubes (MWCNTs), at three percentages, into the urea-formaldehyde (UF) shell-wall of microcapsules on the healing efficiency is reported. The modified shell-wall created a conductive network in semi-conductive epoxies, which led to an improvement of the electromagnetic interference shielding effectiveness (EMI SE); utilizing the excellent electrical properties of the CNTs. The microcapsule's mean diameter and shell wall were examined via scanning electron microscopy (SEM). Thermal stability was evaluated via thermogravimetric analysis (TGA). The healing efficiency was assessed in terms of fracture toughness, while the electrical properties were measured using impedance spectroscopy. The measurements of the EMI SE were carried out in the frequency range of 7–9 GHz. The derived results indicated that the incorporation of the CNTs resulted in a decrease in the mean size of the microcapsules, while the thermal stability remained unchanged. In particular, the introduction of 0.5% w/v CNTs did not affect the healing efficiency, while it increased the initial mechanical properties of the epoxy after the incorporation of the self-healing system by 27%. At the same time, it led to the formation of a conductive network, providing electrical conductivity to the epoxies. The experimental results showed that the SE increased on average 5 dB or more after introducing conductive microcapsules. [ABSTRACT FROM AUTHOR]

In recent years, responsive materials including dynamic bonds have been widely acclaimed due to their expectation to pilot advanced materials. Within these materials, synthetic polymers have shown to be good candidates. Recently, the so-called frustrated Lewis pairs (FLP) have been used to create responsive materials. Concretely, the activation of diethyl azodicarboxylate (DEAD) by a triphenylborane (TPB) and triphenylphosphine (TPP) based FLP has been recently exploited for the production of dynamic cross-links. In this work, we computationally explore the underlying dynamic chemistry in these materials, in order to understand the nature and reversibility of the interaction between the FLP and DEAD. With this goal in mind, we first characterize the acidity and basicity of several TPB and TPP derivatives using different substituents, such as electron-donating and electron-withdrawing groups. Our results show that strong electron-donating groups increase the acidity of TPB and decrease the basicity of TPP. However, the FLP–DEAD interaction is not mainly dominated by the influence of these substituents in the acidity or basicity of the TPB or TPP systems, but by attractive or repulsive forces between substituents such as hydrogen bonds or steric effects. Based on these results, a new material is proposed based on FLP–DEAD complexes. [ABSTRACT FROM AUTHOR]

A furan functionalized epoxy-amine thermoset with an embedded microcapsule healing system that utilizes reversible Diels-Alder healing chemistry was used to investigate the influence of microcapsule loading on healing efficiency. A urea-formaldehyde encapsulation technique was used to create capsules with an average diameter of 150 µm that were filled with a reactive solution of bismaleimide in phenyl acetate. It was found that optimum healing of the thermoset occurred at 10 wt% microcapsule content for the compositions investigated. The diffusion of solvent through the crack interface and within fractured samples was investigated using analytical diffusion models. The decrease in healing efficiency at higher microcapsule loading was attributed partially to solvent-induced plasticization at the interface. The diffusion analysis also showed that the 10% optimum microcapsule concentration occurs for systems with the same interfacial solvent concentration. This suggests that additional physical and chemical phenomena are also responsible for the observed optimum. Such phenomena could include a reduction in surface area available for healing and the saturation of interfacial furan moieties by reaction with increasing amounts of maleimide. Both would result from increased microcapsule loading. [ABSTRACT FROM AUTHOR]

Triboelectric nanogenerators (TENGs) as a revolutionary system for harvesting mechanical energy have demonstrated high vitality and great advantage, which open up great prospects for their application in various areas of the society of the future. The past few years have seen exponential growth in many new classes of self-healing polymers (SHPs) for TENGs. This review presents and evaluates the SHP range for TENGs, and also attempts to assess the impact of modern polymer chemistry on the development of advanced materials for TENGs. Among the most widely used SHPs for TENGs, the analysis of non-covalent (hydrogen bond, metal–ligand bond), covalent (imine bond, disulfide bond, borate bond) and multiple bond-based SHPs in TENGs has been performed. Particular attention is paid to the use of SHPs with shape memory as components of TENGs. Finally, the problems and prospects for the development of SHPs for TENGs are outlined. [ABSTRACT FROM AUTHOR]

Recently, it has been shown that the reaction mechanism in self-healing diphenyl dichalcogenide-based polymers involves the formation of sulfenyl and selenyl radicals. These radicals are able to attack a neighbouring dichalcogenide bond via a three-membered transition state, leading to the interchange of chalcogen atoms. Hence, the chain mobility is crucial for the exchange reaction to take place. In this work, molecular dynamics simulations have been performed in a set of disulfide- and diselenide-based materials to analyze the effect of the molecular structure in the chain mobility. First of all, a validation of the computational protocol has been carried out, and different simulation parameters like initial guess, length of the molecular chains, size of the simulation box and simulation time, have been evaluated. This protocol has been used to study the chain mobility and also the self-healing capacity, which depends on the probability to generate radicals (ρ), the barrier of the exchange reaction ( Δ G ) and the mobility of the chains (ω). The first two parameters have been obtained in previous quantum chemical calculations on the systems under study in this work. After analyzing the self-healing capacity, it is concluded that aromatic diselenides (PD-SeSe) are the best candidates among those studied to show self-healing, due to lower reaction barriers and larger ω values. [ABSTRACT FROM AUTHOR]