The molecular mobility related to the glass transition and secondary relaxations in a hyperbranched polyethyleneimine, HBPEI, and its relaxation behaviour when incorporated into an epoxy resin matrix are investigated by dielectric relaxation spectroscopy (DRS) and dynamic mechanical analysis (DMA). Three systems are analysed: HBPEI, epoxy and an epoxy/HBPEI mixture, denoted ELP. The DRS behaviour is monitored in the ELP system in three stages: prior to curing, during curing, and in the fully cured system. In the stage prior to curing, DRS measurements show three dipolar relaxations: , and , for all systems (HBPEI, epoxy and ELP). The -relaxation for the ELP system deviates significantly from that for HBPEI, but superposes on that for the epoxy resin. The fully cured thermoset displays both - and -relaxations. In DMA measurements, both - and -relaxations are observed in all systems and in both the uncured and fully cured systems, similar to the behaviour identified by DRS.

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