On the use of Ozawa/Flynn/Wall method to determine aging activation energy for elastomers

It is often necessary to assess the effect of aging at room temperature over years/decades for hardware containing elastomeric components such as oring seals or shock isolators. In order to determine this effect, accelerated oven aging at elevated temperatures is pursued. When doing so, it is vital that the degradation mechanism still be representative of that prevalent at room temperature. This places an upper limit on the elevated oven temperature, which in turn, increases the dwell time in the oven. As a result, the oven dwell time can run into months, if not years, something that is not realistically feasible due to resource/schedule constraints in industry. Measuring activation energy (Ea) of elastomer aging by test methods such as tensile strength or elongation, compression set, modulus, oxygen consumption, etc. is expensive and time consuming. Use of kinetics of weight loss by ThermoGravimetric Analysis (TGA) using the Ozawa/Flynn/Wall method per ASTM E1641 is an attractive option (especially due to the availability of commercial instrumentation with software to make the required measurements and calculations) and is widely used. There is no fundamental scientific reason why the kinetics of weight loss at elevated temperatures should correlate to the kinetics of loss of mechanical properties over years/decades at room temperature. Ea obtained by high temperature weight loss is almost always significantly higher than that obtained by measurements of mechanical properties or oxygen consumption over extended periods at much lower temperatures. In this paper, data on five different elastomer types (butyl, nitrile, EPDM, polychloroprene and fluorocarbon) are presented to prove that point. Thus, use of Ea determined by weight loss by TGA tends to give unrealistically high values, which in turn, will lead to incorrectly high predictions of storage life at room temperature.