Communication: Theory of melt-memory in polymer crystallization

Details of crystallization processes of a polymer at the crystallization temperature Tc from its melt kept initially at the melt temperature Tm depend profoundly on the nature of the initial melt state and often are accompanied by memory effects. This phenomenon is in contrast to small molecular systems where the supercooling ( T m 0 − T c ), with T m 0 being the equilibrium melting temperature, and not (Tm − Tc ), determines the nature of crystallization. In addressing this five-decade old puzzle of melt-memory in polymer crystallization, we present a theory to describe melt-memory effects, by invoking an intermediate inhomogeneous melt state in the pathway between the melt and crystalline states. Using newly introduced dissolution temperature T 1 0 for the inhomogeneous melt state and the transition temperature T t 0 for the transition between the inhomogeneous melt and crystalline states, analytical formulas are derived for the nucleation rate as a function of the melt temperature. The theory is general to address different kinds of melt-memory effects depending on whether Tm is higher or lower than T m 0 . The derived results are in qualitative agreement with known experimental data, while making predictions for further experiments on melt-memory.