Ageing and yielding in model epoxy thermosets

The effect of physical ageing on the d.s.c. heat flow and yielding behaviour has been investigated for two series of epoxy resins in which the crosslink density is varied without significant compositional variation. At low degrees of undercooling, the extent of enthalpic ageing approached a thermodynamic limit with increased ageing time, but at larger degrees of undercooling, full densification was not achieved in the time-scale of the experiments due to kinetic control of the ageing process. At constant degree of undercooling, the relaxation enthalpy decreased as the crosslink density was raised, which is attributed to topological restrictions on the process of segmental re-organization leading to densification. However, neither crosslink density nor amine nature appeared to significantly affect the ageing kinetics when measured at the same degree of undercooling. The influence of ageing on the room temperature yield stress was also investigated. Even though the yield stress increased with crosslink density, the influence of ageing on the yield stress was reduced. The time-scales for enthalpic ageing and yield stress enhancement did not appear comparable. (C) 1998 Elsevier Science Ltd. All rights reserved.