Organic monolayers and fluoropolymer brushes : functionalization, stability and tribology

This thesis deals with the adhesion and friction properties of densely grafted and covalently bound fluoropolymer brushes on silicon surfaces with varying thickness and fluorine content. A novel surface-functionalizing method is described using the thiol-yne click (TYC) reaction. The TYC reaction is highly useful for the attachment of functional (bio-)molecules and immobilization of radical initiators onto a surface with high density. Next, the hydrolytic and thermal stability of 24 different types of monolayers on Si(111), Si(100), SiC, SiN, SiO₂, CrN, ITO, PAO, Au and stainless steel surfaces was evaluated. Subsequently, based on this outcome, highly stable fluorinated polymers are described as obtained using surface-initiated atom transfer radical polymerization (SI-ATRP) reactions. The effects of thickness and fluorine content on tribological properties of these layers were studied. The adhesion and friction properties were investigated using colloidal probe atomic force microscopy under dry and ambient conditions. The solvent-free lubricating properties of obtained fluoropolymer brushes have been characterized in detail, and demonstrate their potential for e.g., MEMS/NEMS devices.