There is compelling evidence that the degradation kinetics of thin polymer films differ significantly from those of bulk materials, as interfacial effects become dominant. Therefore, it is crucial to investigate these kinetics separately. Qualitative analytics of thin film degradation exist, e.g. by scanning electron microscopy or atomic force microscopy (AFM), but a quantitative study is so far missing. In this work, poly(sebacic anhydride) (PSA), an aliphatic polyanhydride, is used as a model system for a quantitative degradation study. PSA was spin-coated onto silicon or gold substrates. The degradation of these PSA films was monitored by ellipsometry, surface-plasmon resonance spectroscopy (SPR), and Fourier transform infrared spectroscopy (FTIR). Two kinetic regimes were observed when plotting the relative layer thickness determined by FTIR and SPR against the degradation time. The data obtained by FTIR showed a single process for the rate of ester bond cleavage. Overall, the degradation rate constants of PSA determined by the different methods were consistent. The degradation rate constants of PSA film up to 378 nm thickness were constant. Several thicker free-standing samples studied gravimetrically had a degradation rate constant that was one order of magnitude slower, thus confirming thickness-dependent degradation rate constants.
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