Visualization of two-dimensional single chain conformations solubilized in a miscible polymer blend monolayer by atomic force microscopy.

Polymer Langmuir monolayers spread on a water surface are one of the best models for two-dimensional (2D) polymer and have been extensively studied. However, the most fundamental issue in understanding a 2D film, the polymer chain packing in the film, is still not well-understood, especially from the experimental point of view. Direct observation of the chain packing by microscopy at a molecular level, such as by atomic force microscopy (AFM), might be one of the most promising ways to study this issue; however, because of the limited resolution of the method, the chain packing of polymer cannot be resolved by AFM, except for especially large polymers. Here, we show that a mixed monolayer of vinyl polymers, poly(methyl methacrylate) (PMMA) and poly(n-nonyl acrylate) (PNA), was miscible at a low surface pressure, and if a small amount of PMMA chains was solubilized in a PNA monolayer, the isolated PMMA chains in the PNA monolayer were, for the first time, successfully visualized by AFM with a clear contrast, which originated from a difference of rigidities of the polymers due to their different glass transition temperatures (105 °C(PMMA) and -89 °C(PNA)). The PMMA chains were found to strongly interpenetrate into the PNA monolayer, with a radius of gyration (R(g(PMMA))) that was several times larger than that of the 2D ideal chain (segregated-chain). Furthermore, the radius scaled with the molecular weight of the PMMA (M(PMMA)) as R(g(PMMA)) ∝ M(PMMA)(0.63), which was between the scaling of the 2D ideal chain (segregated chain), R(g) ∝ M(0.5), and the 2D chain in good solvent, R(g) ∝ M(0.75). On the other hand, R(g(PMMA)) was independent of the molecular weight of the PNA matrix over a wide range. These results indicate that the PNA/PMMA monolayer is a strongly miscible system, although the R(g(PMMA)) scaling with M(PMMA) (0.63) is somewhat smaller than that expected for a 2D chain in good solvent systems (0.75). The generation of molecular level information by direct observation of polymer chains in 2D blend films should improve our understanding of polymer 2D films.