Influence of Composition,Humidity, and Temperature on Chemical Aging in Epoxies: A Local Study of the Interphase with Air

The developing chemical depth profile in an epoxy adhesive bulk (with varying amine content) is monitored during aging by FTIR microspectroscopy on sample cuts prepared with low angle microtomy. Three aging regimes are applied in order to separate the role of temperature and water: dried or moist air (90% rel. humidity) at 60°C and dried air at 120°C for up to 300 days. Quantitative evaluation of the IR spectra shows: thermo-oxidative aging (= dried air) is controlled by the diffusion of atmospheric oxygen. It affects a gradient region of more than 200 μm in depth. At given aging time, the depth profiles depend on temperature, humidity, and on the epoxy-amine ratio. Humidity mainly affects the IR band intensities. The plasticizing effect of water promotes the loss of small network fragments. At 120°C, autoxidation of α-CH₂ at ether and amine groups and the oxidative attack on tertiary amines dominate aging. At 60°C in dried air, these processes proceed only very slowly. In the case of amine excess, aging is extended by the additional oxidation of primary and secondary amines to carbonyls. Carbonyls undergo consecutive reactions, especially in the presence of water. Hence, increasing temperature does not simply accelerate the aging mechanisms but it reduces their selectivity and changes their hierarchy. Thus, the long-term aging behavior at moderate temperatures cannot be predicted safely from accelerated aging tests.