This review outlines latest developments in the field of self-healing rubbers and elastomers, analyzing their potential application to natural rubber (NR). Different validated healing concepts are presented and the possibilities of applying them to NR are discussed. Research in this field should aim at modifying the chemical structure of NR as to enhance physical or chemical reversible interactions either intermolecular or intramolecular. The realization of better mechanical properties at relevant working conditions and with milder healing conditions remains a challenge for all self-healing rubbers. This overview should be seen as setting the conceptual framework for new developments with a more clearly defined industrial focus.

@en

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 Havriliak−Negami 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 self-healing polymer systems with prospective applications such as coatings, tires, seals, and gaskets. @en

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 @en

In this work we report the effect of the hard block dianhydride structure on the overall properties of partially bio-based semi-aromatic polyimides. For the study, four polyimides were synthesized using aliphatic fatty dimer diamine (DD1) as the soft block and four different commercially available aromatic dianhydrides as the hard block: 4,4'-(4,4'-isopropylidenediphenoxy) bis-(phthalic anhydride) (BPADA), 4,4'-oxydiphthalic anhydride (ODPA), 4,4′-(Hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA). The polymers synthesized were fully organo-soluble thermoplastic branched polyimides with glass transition temperatures close to room temperature. The detailed analysis took into account several aspects of the dianhydrides structure (planarity, rigidity, bridging group between the phtalimides, electronic properties) and related them to the results obtained by differential scanning calorimetry, rheology, fluorescence and broadband dielectric spectroscopy. Moreover, the effect of physical parameters (crystallization and electronic interactions) on the relaxation behavior are discussed. Despite the presence of the bulky branched soft block given by the dimer diamine, all polyimides showed intermolecular charge transfer complexes, whose impact depends on the electronic properties of the dianhydride hard block. Furthermore, the results showed that polyimides containing flexible and bulky hard blocks turned out fully amorphous while the more rigid dianhydride (BPDA) led to a nanophase separated morphology with low degree of crystallinity resulting in constrained segmental relaxation with high effect on its mechanical response with the annealing time. This work represents the first detailed report on the development and characterization of polyimides based on a bio-based fatty dimer diamine. The results highlight the potential of polymer property design by controlled engineering of the aromatic dianhydride blocks. @en

Miscible S-SBR (solution styrene-butadiene copolymer)/BR (polybutadiene homopolymer) blends are used in multiple applications like modern passenger car tire treads. Despite their miscibility, there is a problem to predict tire performance due to dynamical heterogeneities present in the S-SBR/BR blends. On the one hand, S-SBR/BR blends have a thermorheologically complex behavior, which complicates the prediction of the temperature- and frequency-dependence of material properties. On the other hand, due to differences in the polarity of the individual components, the extender oils used in the elastomeric compounds could distribute unequally within the blends, where little is known about how oils interact with the two polymers. In this work a combination of Differential Scanning Calorimetry, Dynamic Mechanical Analysis, and Broadband Dielectric Spectroscopy (BDS) is used to clarify: (i) the thermorheological complexity of S-SBR/BR blends, (ii) the effect of the extender oil on the blend. The broad frequency operation of BDS allows for the analysis of the S-SBR and BR component dynamics and the effect of the oil on each of them within an S-SBR/BR (50/50) blend. Based on the discretization of individual component dynamics in the blend, conclusive remarks are made on the effect of the extender oil for either component in the blend.

@en

Miscible S-SBR (solution styrene-butadiene copolymer)/BR (polybutadiene homopolymer) blends are used in multiple applications like modern passenger car tire treads. Despite their miscibility, there is a problem to predict tire performance due to dynamical heterogeneities present in the S-SBR/BR blends. On the one hand, S-SBR/BR blends have a thermorheologically complex behavior, which complicates the prediction of the temperature- and frequency-dependence of material properties. On the other hand, due to differences in the polarity of the individual components, the extender oils used in the elastomeric compounds could distribute unequally within the blends, where little is known about how oils interact with the two polymers. In this work a combination of Differential Scanning Calorimetry, Dynamic Mechanical Analysis, and Broadband Dielectric Spectroscopy (BDS) is used to clarify: (i) the thermorheological complexity of S-SBR/BR blends, (ii) the effect of the extender oil on the blend. The broad frequency operation of BDS allows for the analysis of the S-SBR and BR component dynamics and the effect of the oil on each of them within an S-SBR/BR (50/50) blend. Based on the discretization of individual component dynamics in the blend, conclusive remarks are made on the effect of the extender oil for either component in the blend.

@en

In the present work we show the effect of graphene loading on the restoration of the mechanical properties and thermal and electrical conductivity of a self-healing natural rubber nanocomposite. The graphene loading led to a minimal enhancement of mechanical properties and yielded a modest increase in thermal and electrical conduction. The polymer nanocomposites were macroscopically damaged (cut) and thermally healed for 7 h in a healing cell. Different healing trends as function of the graphene content were found for each of the functionalities: (i) thermal conductivity was fully restored independently of the graphene filler loading; (ii) electrical conductivity was only restored to a high degree above the percolation threshold; and (iii) tensile strength restoration increased more or less linearly with graphene content but was never complete. A dedicated molecular dynamics analysis by dielectric spectroscopy of the pristine and healed samples highlighted the role of graphene-polymer interactions at the healed interphase on the overall restoration of the different functionalities. Based on these results it is suggested that the dependence of the various healing efficiencies with graphene content is due to a combination of the graphene induced lower crosslinking density, as well as the presence of strong polymer-graphene interactions at the healed interphase.@en

In the present work we show the effect of graphene loading on the restoration of the mechanical properties and thermal and electrical conductivity of a self-healing natural rubber nanocomposite. The graphene loading led to a minimal enhancement of mechanical properties and yielded a modest increase in thermal and electrical conduction. The polymer nanocomposites were macroscopically damaged (cut) and thermally healed for 7 h in a healing cell. Different healing trends as function of the graphene content were found for each of the functionalities: (i) thermal conductivity was fully restored independently of the graphene filler loading; (ii) electrical conductivity was only restored to a high degree above the percolation threshold; and (iii) tensile strength restoration increased more or less linearly with graphene content but was never complete. A dedicated molecular dynamics analysis by dielectric spectroscopy of the pristine and healed samples highlighted the role of graphene-polymer interactions at the healed interphase on the overall restoration of the different functionalities. Based on these results it is suggested that the dependence of the various healing efficiencies with graphene content is due to a combination of the graphene induced lower crosslinking density, as well as the presence of strong polymer-graphene interactions at the healed interphase.@en