ABSTRACT:The thermal and hydro-thermal aging of a hot-cured epoxy system (diglycidylether of bisphenol A (DGEBA) ϩ dicyandiamide (DDA)) in the glassy state is revisited using DSC and IR attenuated total reflection spectroscopy. Because of the diffusion of DDA from the solid particles into the liquid DGEBA matrix, curing produces a highly crosslinked amorphous matrix that contains low crosslinked amorphous regions. After full curing, the network possesses a relatively low molecular mobility and no residual reactive groups. Thermal and hydro-thermal loading is performed at 60°C, well below the principal glass transition temperature (T g1 ϭ 171°C). Both aging regimes cause significant chemical and structural changes to the glassy epoxy. It undergoes a phase separation of relatively mobile segments inside the low mobile matrix, providing a second glass transition that shifts from T g2 ϭ 86 -114°C within 108 days of aging. This phase separation is reversible on heating into the viscoelastic state. Hydro-thermal aging leads to a reversible and a nonreversible plasticizing effect as well. On thermal aging, no chemical changes are observed but hydro-thermal aging causes significant chemical modifications in the epoxy system. These modifications are identified as a partial degradation of crosslinks produced by the cyano groups of the DDA and correspond to the nonreversible plasticitation. These changes in the cured epoxy should exert an influence on the mechanical properties of an adhesive bond.