Fast surface diffusion of amorphous o-terphenyl and its competition with viscous flow in surface evolution.

Abstract

Surface self-diffusion coefficients have been measured for the model molecular glass o-terphenyl (OTP) through surface-grating decay driven by capillarity. The decay mechanism transitions from viscous flow at high temperatures to surface diffusion at low temperatures; for 1000 nm wavelength gratings, the transition occurs at Tg + 11 K. The surface diffusion of OTP is 10(8) times faster than bulk diffusion at Tg and even faster at lower temperatures because of its weaker temperature dependence. At Tg, OTP has approximately the same bulk diffusivity as the previously studied molecular liquid indomethacin, but its surface diffusion is 100 times faster. While the molecular glass-formers exhibit transitions from viscous flow to surface diffusion as the mechanism of capillarity-driven surface flattening, polystyrenes and silicates show no such transition under comparable conditions, suggesting slower surface diffusion on these materials and a general dependence of surface diffusion on intermolecular forces. The velocity of surface crystal growth on molecular glasses is proportional to surface diffusivity, indicating a common kinetic barrier for both processes for temperatures below Tg.