The effect of a secondary process on crystallization kinetics – Poly (є-caprolactone) revisited

Abstract It is suggested that the overlap of primary and secondary crystallization is a cause of the repeated observation of non-integer n values in polymer crystallization. The possibility that two concurrent crystallization processes occurring during the crystallization of poly (є-caprolactone), and polymers in general, may account for anomalous fractional values of the Avrami exponent, of no theoretical significance, is reconsidered using data from the recent evaluation of the kinetics of crystallization which placed emphasis on evaluating the secondary crystallization stage. In general constant n values in excess of that expected for the crystallization mechanisms could readily be interpreted in terms of the additional crystallinity developed by the secondary process and these values increased commensurate with the rate constant of secondary crystallization.