In situ probing of switchable nanomechanical properties of responsive high-density polymer brushes on...

Nanomechanical characteristics of end grafted polymer brushes were studied by AFM based, colloidal probe nanoindentation measurements. A high-density polymer brush of poly(2-hydroxyethyl methacrylate) (PHEMA) was precisely prepared on the surface of a flexible poly(dimethylsiloxane) (PDMS) substrate oxidized in ultraviolet/ozone (UVO). Exposure times less than 10min resulted in laterally homogeneous oxidized surfaces, characterized by a SiO_x thickness ∼35nm and an increased modulus up to 9MPa, as shown by AFM nanoindentation measurements. We have demonstrated that a high surface density of up to ∼0.63chains/nm² of the well-defined PHEMA brushes can be grown from the surface of oxidized PDMS by surface-initiated atom transfer radical polymerization (SI-ATRP) from trimethoxysilane derivatives mixed-SAM. The reversible nanomechanical changes of PHEMA layer between extended (hydrated state) and collapsed (dehydrated state) chain upon immersing in selective and non-selective solvents were investigated by in situ AFM nanoindentation analysis in liquid environments. The elastic modulus derived from force-indentation curves obtained for swollen PHEMA grafted chains in water was estimated to be equal 2.7±0.2MPa, which is almost two orders of magnitude smaller than the modulus of dry PHEMA brush. Additionally, under cyclohexane immersion, the modulus of the PHEMA layer decreased by one order of magnitude, indicating a more compact chain packing at the PDMS surface.