Origin of enhanced crystal growth kinetics near Tg probed with indomethacin polymorphs.

Using three crystal polymorphs of indomethacin (IMC), we tested two interpretations of the enhanced crystal growth kinetics near the glass transition temperature Tg. This enhancement refers to the stronger temperature dependence of liquid viscosity eta than crystal growth rate (corrected for thermodynamic driving force). This enhancement is attributed in the first interpretation to an increase of the number of preferred interfacial growth sites with decreasing temperature and, in the second interpretation, to the breakdown of the Stokes-Einstein relation in deeply supercooled liquids. We measured the growth rates of the IMC polymorphs (alpha, gamma, and delta) from Tg + 9 K (Tg = 314 K) to near the respective melting points. From Tg + 19 K to Tg + 69 K, the growth rates of the polymorphs changed by 10(4) fold but displayed the same temperature dependence (eta-0.78) after corrections for thermodynamic driving forces. These results argue for a liquid-state origin of the enhanced growth kinetics. Below ca. Tg + 19 K, delta IMC continued to grow in the same spherulite morphology but alpha and gamma IMC grew in different, fiberlike morphologies and, if measured consistently, at faster rates. We conclude that the liquid dynamics of IMC controls its crystal growth kinetics over a wide range of temperatures but changes of growth morphologies near Tg also lead to apparent acceleration of growth of certain polymorphs. This work also extended a previous study of D-sorbitol to lower temperatures to enable a broader analysis of crystal growth kinetics of organic molecules near Tg.