Fast Surface Diffusion and Crystallization of Amorphous Griseofulvin.

Among molecular glasses, griseofulvin (GSF) is one of the fastest crystallizing. To understand this property, we have measured the surface diffusion in GSF using the method of surface grating decay. Surface diffusion in amorphous GSF is extremely fast, outpacing bulk diffusion by a factor of 108 at the glass transition temperature Tg (361 K). Among all molecular glasses studied (13 in all), GSF has the second fastest surface diffusion (to o-terphenyl) when compared at Tg. The GSF result fits the overall trend for molecular glasses without intermolecular hydrogen bonds, where surface diffusion systematically slows down with increasing molecular size. This result is particularly noteworthy because GSF has many hydrogen-bond acceptors but no donors, indicating that, so long as they do not participate in hydrogen bonding, the polar functional groups have a similar effect on surface diffusion as the nonpolar hydrocarbon groups. In contrast, the formation of intermolecular hydrogen bonds strongly inhibits surface diffusion. The surface crystal growth rate of amorphous GSF is nearly proportional to its surface diffusion coefficient, as noted for other systems, supporting the view that surface crystal growth is controlled by surface diffusion. In addition, the fast surface diffusion of GSF glasses explains the fast crystal growth along fracture surfaces and suggests a basis to understand fast crystal growth in the bulk through continuous creation of microcracks.