Probing photodegradation beneath the surface: a depth profiling study of UV-degraded polymeric coatings with microchemical imaging and nanoindentation

Photodegradation of polymer coatings generally involves photooxidation, resulting in the formation of oxidized products, chain scission, and crosslinking. On severe exposure to ultraviolet (UV) light in the presence of air, chemical degradation transforms into substantial changes in the physical and mechanical properties, leading to failures of the coatings. Systematic research by NIST on service life prediction of polymeric coatings indicates that the degradation of polymer coatings starts from the sub-micrometer degradation-susceptible regions at the surface and then grows in width and depth. Additionally, due to the oxygen diffusion effect and the attenuation of the UV light passing through the polymer, the degradation can be spatially heterogeneous. In this study, the changes with depth of the mechanical and chemical properties of a UV-exposed epoxy/polyurethane system were measured by nanoindentation and Fourier transform infrared spectroscopy (FTIR) microscopy using cross-sectioned specimens. Multilayers of epoxy/polyurethane samples were prepared by a draw-down technique. After curing, samples were exposed to the outdoors in Gaithersburg, MD, for four months. Cross-sectioned slices of the exposed and unexposed samples, approximately 500 nm thick as-prepared by microtoming, were used for micro-FTIR imaging. Samples for nanoindentation were prepared by embedding the epoxy/polyurethane multilayers (both exposed and unexposed) in a molding compound, followed by microtoming and polishing the embedded films in the thickness direction. Micro-FTIR images clearly show that, for the outdoor exposed samples, substantial amounts of oxidation products are distributed in the 60 μm deep region from the surface to the epoxy bulk, decreasing in the center of epoxy region and increasing again toward the epoxy/urethane interface. Nanoindentation results also show that the modulus significantly increases in the first 60 μm region after UV degradation, and then decreases gradually with depth until a value slightly higher than the modulus of the undegraded epoxy is reached. The modulus rises again in the region near the epoxy/urethane interface. These similarities in the depth profiles of the properties indicate the linkage between the chemical degradation and the mechanical degradation. The study clearly shows that the spatial distribution of chemical species and mechanical properties is heterogeneous in the thickness direction for polymer coatings after UV degradation. It also demonstrates that cross-sectional analysis using nanoindentation and micro-FTIR imaging techniques is a useful method to characterize the mechanical and chemical depth profiles of polymer coating degradation.