In-situ interfacial approaches on chemisorption and stability of buried metal oxide-polymer interfaces

Until today, interfacial bond formation and degradation between polymer coatings and metal substrates is still far from fully understood, whilst it is a limiting factor for the durability of metal-polymer hybrid systems. To improve the corrosion resistance and adhesion properties of metal substrates, a chemical surface treatment is applied prior to painting. However, due to ecological and health related issues, traditional well established surface treatments containing hexavalent chromate or high phosphate loads are being replaced by a new generation of ecologically-justified surface treatments. This comes with the need of gaining fundamental insights on the impact of substrate and pretreatment variations on the (chemical) adhesion of polymers to guarantee the lifetime of newly developed metal-polymer hybrid systems. A challenge in this regard is the hardly accessible buried interface, which until today requires the use of model systems when using non-destructive surface sensitive techniques. Yet, industrial metal-polymer hybrid systems are typically highly heterogeneous, creating a distinct gap between model and industrial systems. This dissertation aims to close this gap starting from simplified model systems to which complexity is gradually added. This has been done using the thin organic film approach on one hand, and the thin (thermally vaporized) metal substrate approach on the other hand, allowing non-destructive access of the metal-polymer interface from the polymer side and metal side, respectively. Complementary use of both approaches allows systematically comparison of model systems to industrially relevant paint and metal substrates.