A class of poly(ethylene-co-methacrylic acid) (EMAA) copolymers and ionomers has shown the unique ability to instantaneously self-heal following ballistic puncture. It is noteworthy that the thermomechanical healing process active in these materials appears to be significantly different in capability and mechanism than any of the other self-repairing systems studied. To better understand this phenomenon, the thermal response during EMAA self-healing was examined. Tests of various damage types, including sawing, cutting and puncture, revealed high-energy transfer damage modes to produce heat and store energy favourable to healing. DSC probed healed specimens revealing they had reached the viscoelastic melt believed requisite to healing response. Low-temperature ballistic experiments demonstrated films continue healing even when punctured at K308C; analysis showed healing efficacy comparable to room temperature, holding significant pressures of approximately 3 MPa. At the lowest temperature, brittle fracture occurred in one material indicating insufficient heat transfer to store recoverable energy. In total, the results supported the defined healing model and provided additional information on the healing process in both its thermal dependence and general mechanism. Finally, a new DSC method was developed for probing the thermal history of healed films which may lead to a more complete mechanistic model.

No abstract

No abstract

Solid-state healing of epoxy networks is shown to be an effective and robust mechanism for highly cross-linked epoxy networks. Using diglycidyl ether of bisphenol A epoxy resin and diethyltoluenediamine, the cured epoxy network is transformed into a mendable system using phenoxy resin and low-molecular-weight polybisphenol A-co-epichlorohydrin) thermoplastic modifiers. Using functionally terminated low-molecular-weight poly(bisphenol A-co-epichlorohydrina) thermoplastic modifiers as healing agents reveals that salicylic acid or neutralized sodium salicylate groups produce healing similar to high-molecular-weight non-functional phenoxy resin as measured using single-end notched beam testing. The miscibility of both thermoplastics in the diglycidyl ether of bisphenol A/diethyltoluenediamine system was evaluated using differential scanning calorimetry and dynamic mechanical thermal analysis and identified as being important to promoting healing. Near-infrared spectroscopy showed that the network structure was unaffected by the thermoplastic modification, suggesting that healing occurred primarily through physical or non-covalent mechanisms rather than covalent bonding. The potential for self-assembly of the salicylic acid and neutralized sodium salicylate groups to form a high-molecular-weight thermoplastic in situ was also discussed as being a possible reason for the improved level of healing with the low-molecular-weight thermoplastic.