In Situ Real-Time Atomic Force Microscopy Observations of Chain Mobility at Polymer/Water Interfaces of Poly(methyl...

Polymer materials are widely used in water or in contact with an aqueous environment. However, evaluating the chain mobility, a crucial parameter, at a polymer-water interface is challenging. In this study, we, for the first time, observed poly(methyl methacrylate) (PMMA), poly(2-hydroxyethyl methacrylate) (PHEMA), and poly(2-methoxyethyl methacrylate) (PMEMA) film surfaces in water via in situ real-time atomic force microscopy (AFM) in tapping mode and quantified the chain mobility. The average displacement between adjacent images (nm/8.75 min) was evaluated using particle image velocimetry. The displacement of PMMA, which has a high bulk glass-transition temperature (T_g) (108 °C) and exhibits limited water absorption, was low both in air (0.54 nm/8.75 min) and water (0.86), while PHEMA, which has a high bulk T_g (99 °C) and exhibits high water absorption, exhibited low mobility in air (0.40) but two orders of magnitude higher mobility in water (60). PMEMA, which has a low bulk T_g (14 °C) and exhibits limited water absorption, already started to move in air (4.5), and its mobility moderately increased in water (20). These behaviors were reasonable, considering the bulk T_g and water absorption characteristics of the polymers. Further, the chain mobility in water was compared with that of dried samples at high temperatures in air. The mobility of PMMA, PHEMA, and PMEMA in water corresponded to that of the dried samples observed in air below the surface T_g (97 °C) for PMMA, at ∼125 °C for PHEMA, and at ∼35 °C for PMEMA. In situ real-time AFM analysis of polymer materials in water is an effective method for evaluating the chain mobility at the polymer/water interface.