Probing hidden polymeric interfaces using IR-visible sum-frequency generation spectroscopy

Understanding the molecular-level processes underlying interfacial phenomena is important in the area of adhesion. We briefly introduce IR-visible sum-frequency generation spectroscopy (SFG) using a total-internal-reflection geometry for the study of polymer-air, polymer-solid, and polymer-polymer interfaces. The following examples, predominantly of work done in our lab, illustrating differences in molecular structure and dynamic properties at interfaces are presented: the air- and solid-interface structure of an amorphous polystyrene (PS) and a semicrystalline polymer with side-chain crystallinity, poly(octadecyl acrylate) (PA-18); structure of a polymer-polymer interface between thin films of a semicrystalline polymer with side-chain crystallinity, poly(vinyl-N-octadecylcarbamate-co-vinyl acetate), and an amorphous PS; thermal order-to-disorder transitions of the air and solid interface of PA-18, and the interface of this polymer with PS; and dynamic surface-relaxation studies of a rubbed PS film.