Upon decreasing thicknesses, polymer layers can exhibit properties distinct from their bulk counterparts. It is critical to understand and control the structure and properties of polymer layers under confinement for their success in applications. Significant efforts have been taken to manipulate chain conformations in polymer nanolayers and examine their resulting effects on material properties. Building on these endeavors, this dissertation focuses on polymer films in three diverse morphologies: spin-coated films, polymer brushes, and polymer adsorbed layers.

The majority of this dissertation examines polymer brushes, i.e., thin films composed of polymer chains end-grafted by a single end to a substrate. Polymer brushes can feature unique material properties that distinguish them from spin-coated films. Notably, polymer brushes enable independent manipulation of thickness and chain packing through variation of grafting density (σ).  This dissertation first explores the synthetic pathways for fabricating polymer brush films, including an extension of one approach to develop poly(sulfobetaine methacrylate) (PSBMA)
brush antifouling layers for water treatment applications.  

While polymer brushes have been studied for their antifouling properties, their glassy state behavior, specifically their physical aging, remains unexplored. In this work, we measured the physical aging of both polymer brushes at varying σ and spin-coated films at different aging temperatures (Ta) using ellipsometry. At low film thicknesses and high Ta, poly(methyl methacrylate) (PMMA) and polystyrene (PS) brushes exhibited heightened physical aging rates relative to similarly thick spin-coated films. At low Ta, thin PS brushes at high values of σ had lower physical aging rates than their spin-coated counterparts. Our results demonstrate that morphology can indeed impact the physical aging of polymer films. 

Apart from polymer brushes, this dissertation focuses on polymer adsorption on curved surfaces, modulated by the size of silica nanoparticles (SiNPs). The materials of interest are PS, PMMA, and their random copolymers. The adsorbed layer thickness (hp) increased and decreased for PS and PMMA with decreasing SiNP size, respectively. Copolymer systems showed minimal hp dependence on curvature under mild annealing but displayed curvature sensitivity under high annealing conditions. Taken together, this dissertation can inform the design and integration of polymer nanolayers with predictable structures and properties.