Measurement of nanoscale molten polymer droplet spreading using atomic force microscopy

We present a technique for measuring molten polymer spreading dynamics with nanometer scale spatial resolution at elevated temperatures using atomic force microscopy (AFM). The experimental setup is used to measure the spreading dynamics of polystyrene droplets with 2 μm diameters at 115-175 °C on sapphire, silicon oxide, and mica. Custom image processing algorithms determine the droplet height, radius, volume, and contact angle of each AFM image over time to calculate the droplet spreading dynamics. The contact angle evolution follows a power law with time with experimentally determined values of -0.29 ± 0.01, -0.08 ± 0.02, and -0.21 ± 0.01 for sapphire, silicon oxide, and mica, respectively. The non-zero steady state contact angles result in a slower evolution of contact angle with time consistent with theories combining molecular kinetic and hydrodynamic models. Monitoring the cantilever phase provides additional information about the local mechanics of the droplet surface. We observe local crystallinity on the molten droplet surface, where crystalline structures appear to nucleate at the contact line and migrate toward the top of the droplet. Increasing the temperature from 115 °C to 175 °C reduced surface crystallinity from 35% to 12%, consistent with increasingly energetically favorable amorphous phase as the temperature approaches the melting temperature. This platform provides a way to measure spreading dynamics of extremely small volumes of heterogeneously complex fluids not possible through other means.