Surface Mechanical Properties of Thin Polymer Films Investigated by AFM in Pulsed Force Mode

Atomic force microscopy in the pulsed force mode, (PFM) is applied in this work to the study of thin dewetting patterns formed by drying an aqueous solution of poly(N-isopropylacrylamide) (PNIPAM) and sodium dodecyl sulfate (SDS) on mica. This technique allows the automated acquisition of typically 4 x 10(6) force-distance curves on the sample surface together with maps showing nanodomains differentiated by their stiffness and adhesion to the tip. Topography images of dry films revealed a morphology formed by droplets distributed on the substrate. Adhesion and stiffness images with good lateral resolution show droplets containing polymer and surfactant contrasting with the substrate and also nanosized heterogeneities inside these droplets. They also revealed very small dewetted structures which could not be observed in the topography map by noncontact AFM. Adhesion interactions between the AFM tip and the polymer or the dewetted mica substrate were measured in terms of adhesion force and detachment energy, and can be used as new information 10 understand dewetting patterns containing silica particles, PNIPAM. and SDS. Other surface mechanical parameters such as stiffness, maximum indentation, hardness, compliance, hysteresis and Young's modulus were obtained by sampling many points and used to characterize the PNIPAM/SDS films formed in the dewetting process.