A self-healing sulfur vulcanized natural rubber (NR) is here reported using the common ingredients in a traditional NR formulation. The dynamic character of the di- and polysulfide bonds naturally present in covalently cross-linked rubbers was found to be responsible for the healing ability and the full recovery of mechanical properties at moderate temperatures provided the material was employed in a nonfully cured starting state. Results show that a compromise between mechanical performance and healing capability can be reached by tailoring the amount of sulfur, the cross-linking density, and the disulfide/polysulfide ratio. The healing efficiency was found to depend on the postcuring storage time, the time between damage creation and re-establishment of mechanical contact, and the actual healing time. Furthermore, a dedicated electron spin resonance (ESR) test allowed establishing the underlying healing principle based on temperature-induced free sulfur radicals. The main observations presented here can serve as the basis for the design and preparation of other self-healing polymers with long-term durability based on di-/polysulfide bridges and other reversible moieties

Traditional polyetherimides (PEIs) are commonly synthesized from an aromatic diamine and an aromatic dianhydride (e.g. 3,4'-oxydianiline (ODA) and 4,4'-oxydiphtalic anhydride (ODPA)) leading to the imide linkage and outstanding chemical, thermal and mechanical properties yet lacking any self-healing functionality. In this work, we have replaced the traditional aromatic diamine by a branched aliphatic fatty dimer diamine (DD1).This led to a whole family of self-healing polymers not containing reversible chemical bonds, capable of healing at (near) room temperature yet maintaining very high elastomeric-like mechanical properties (up to 6 MPa stress and 570% strain at break). In this work, we present the effect of the DD1/ODPA ratio on the general performance and healing behavior of a room temperature healing polyetherimide. A dedicated analysis suggests that healing proceeds in three steps: (i) an initial adhesive step leading to the formation of a relatively weak interface; (ii) a second step at long healing times leading to the formation of an interphase with different properties than the bulk material and (iii) disappearance of the damaged zone leading to full healing. We argue that the fast interfacial adhesive step is due to van der Waals interactions of long dangling alkyl chains followed by an interphase formation due to polymer chain interdiffusion. An increase in DD1 ratio leads to an increase in the healing kinetics and displacement shift of the first healing step towards lower temperatures. An excess of DD1 leads to the crosslinking of the polymer thereby restricting the necessary mobility for the interphase formation and limiting the self-healing behavior. The results here presented offer a new route for the development of room temperature self-healing thermoplastic elastomers with improved mechanical properties using fatty dimer diamines.

Broadband dielectric spectroscopy (BDS) is introduced as a new and powerful technique to monitor network and macroscale damage healing in an elastomer. For the proof of concept a partially cured sulfur-cured natural rubber (NR) containing reversible disulfides as the healing moiety was employed. The forms of damage healed and monitored were an invisible damage in the rubber network due to multiple straining and an imposed macroscopic crack. The relaxation times of pristine, damaged and healed samples were determined and fitted to the HavriliakNegami equation to obtain the characteristic polymer parameters. It is shown that seemingly full mechanical healing occurred regardless the type of damage, while BDS demonstrates that the polymer architecture in the healed material differs from that in the original one. These results represent a step forward in the understanding of damage and healing processes in intrinsic selfhealing polymer systems with prospective applications such as coatings, tires, seals and gaskets.

This article reviews some of the intrinsic self-healing epoxy materials that have been investigated throughout the course of the last twenty years. Emphasis is placed on those formulations suitable for the design of high-performance composites to be employed in the aerospace field. A brief introduction is given on the advantages of intrinsic self-healing polymers over extrinsic counterparts and of epoxies over other thermosetting systems. After a general description of the testing procedures adopted for the evaluation of the healing efficiency and the required features for a smooth implementation of such materials in the industry, different self-healing mechanisms, arising from either physical or chemical interactions, are detailed. The presented formulations are critically reviewed, comparing major strengths and weaknesses of their healing mechanisms, underlining the inherent structural polymer properties that may affect the healing phenomena. As many self-healing chemistries already provide the fundamental aspects for recyclability and reprocessability of thermosets, which have been historically thought as a critical issue, perspective trends of a circular economy for self-healing polymers are discussed along with their possible advances and challenges. This may open up the opportunity for a totally reconfigured landscape in composite manufacturing, with the net benefits of overall cost reduction and less waste. Some general drawbacks are also laid out along with some potential countermeasures to overcome or limit their impact. Finally, present and future applications in the aviation and space fields are portrayed.

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The development of materials with the ability of intrinsic self-repairing after damage in a fashion resembling that of living tissues has important scientific and technological implications, particularly in relation to cost-effective approaches toward damage management of materials. Natural rubbers with epoxy functional groups in the macromolecular chain (ENR) and ethylene-methacrylic acid ionomers having acid groups partially neutralized with metal ions possess self-repairing behavior following high energy impacts. This research investigates the self-repairing behavior of both ENR and ionomers during ballistic puncture test on the basis of their thermal and mechanical properties. Heterogeneous blending of ionomers and ENR have also been used here as a strategy to tune the thermal and mechanical properties of the materials. Interestingly, blends of sodium ion containing ionomer exhibit complete self-repairing behavior, whereas blends of zinc ion containing ionomer show limited mending. The chemical structure studied by FTIR and thermal analysis shows that both ion content of ionomer and functionality of ENR have significant influence on the self-repairing behavior of blends. The mobility of rubbery phases along with its interaction to ionomer phase in the blends significantly changes the mending capability of materials. The healing behavior of the materials has been discussed on the basis of their thermal, mechanical, and rheological tests for each materials.