Lifetime prediction and degradation assessment of FKM and FFKM O-rings under high temperature thermo-oxidative ageing

To support the development of solar reactor technologies for hydrogen production, this study investigates the thermo-oxidative degradation mechanisms of fluorinated elastomers and predicts their lifetimes at high temperatures (200–300 °C) consistent with the application requirements. An accelerated ageing programme is conducted with FKM and FFKM O-rings and flat samples for up to 21 days. Optical microscopy is used to analyse the exposed seals' morphological changes, while IR microscopy is utilised to investigate the underlying chemical degradation mechanisms of both elastomers. Findings suggest that FKM's degradation arises from dehydrofluorination of the polymer, followed by chain scission and backbone cleavage as a result of the oxidation of newly formed C=C double bonds. FFKM's degradation is primarily associated with chain scission, but there is also indication that post-curing processes may occur during material ageing. Furthermore, hardness, equilibrium compression set (CS), continuous compression stress relaxation (CSR) and leakage rate tests are used to evaluate changes in the mechanical properties and sealing performance of the elastomers. Equilibrium CS data is extrapolated using time-temperature shifts (TTS) and used to derive an end-of-life criterion of 75 % equilibrium CS, which correlates to leakage rates higher than a predetermined threshold. Service lifetime predictions of FKM and FFKM O-rings at several temperatures are performed and a seal operating temperature of 200 °C is suggested, which ensures reasonable O-ring replacement intervals of more than half a year in the solar reactor for both considered materials. • Thermo-oxidative degradation mechanisms of FKM and FFKM elastomers are investigated. • Distinct degradation pathways: dehydrofluorination in FKM and chain scission in FFKM. • Realised hardness, compression set, compression stress relaxation and leakage rate tests. • Lifetime predictions utilised compression set data and time-temperature shifts. • End-of-life criterion was derived as 75 % compression set.