Quantitative spectroscopic analysis of weathering of polyester-urethane coatings

We showed that the degradation of urethane groups proceeds via photo-oxidative pathways and that the ester groups mainly degrade via photolytic reactions. The ester bond scission accelerates after an initially-slow-rate stage of weathering in the presence of urethane groups. This is due to an increase in the optical absorptivity of the coating as a result of degradation under anaerobic conditions, as shown before. By means of a kinetic analysis using a combination of FTIR and UV-Vis spectroscopy results (obtained before), we found that a first-order kinetic model can perfectly describe the rate of ester bond scission during the weathering and that the increase in the rate of reaction is due to the increase in the light absorptivity of the coating as a result of degradation. Finally, using the interference fringes of FTIR spectra, we showed that evaporation and water-caused removal of degraded material cause a particularly pronounced decay in the thickness of the coating. In the absence of water spray, the material loss takes place in the same period as urethane groups decompose and stops afterwards, even though the ester bond scission proceeds with higher rates. This supports the hypothesis of photo-oxidative pathways for the urethane group decomposition and photolytic mechanisms for ester bond scission. Dark experiments showed that PUC coatings are highly resistant to hydrolysis and thermal degradation.