Temperature-Reversible Ultrathin Films of N-Isopropylacrylamide Terpolymer Adsorbed at the Solid−Liquid Interface

This article describes the stability and reversibility of ultrathin films of N-isopropylacrylamide (NIPA)−vinylimidazole (VI)−poly(ethylene glycol) (PEG) graft terpolymer adsorbed at the solid−liquid interface upon temperature cycling from below to above its phase transition temperature. The coil-to-globule and globule-to-coil phase transitions were captured by in situ fluid tapping atomic force microscopy (AFM). The film thickness of 1 nm was determined by AFM, X-ray photoelectron spectroscopy, and X-ray reflectivity. The concentration required to reach full coverage was found to be higher when adsorption occurred below the phase transition temperature. From 23 to 42 °C, the adsorbed NIPA terpolymer film was observed to be molecularly smooth, corresponding to the close-packed structure of flexible polymer coils. Particles containing between one and a few globules appeared abruptly at the interface at 42−43 °C, the same temperature as the solution phase transition temperature, which was determined by dynamic light scattering. The size of the particles did not change with temperature, whereas the number of particles increased with increasing temperature up to 60 °C. The particles correspond to the collapsed and associated state of the globules. The film morphological changes were found to be reversible upon temperature cycling. Subtle differences were observed between dip-coated and spin-coated films that are consistent with a higher degree of molecular freedom for spin-coated films. The study contributes to the fundamental understanding and applications of smart ultrathin films and coatings.