The Effect of a Secondary Process on the Analysis of Isothermal Crystallisation Kinetics by Differential Scanning Calorimetry

This paper demonstrates the application of a modified Avrami equation in the analysis of crystallisation curves obtained using differential scanning calorimetry (DSC). The model incorporates a square root of time dependence of the secondary process into the conventional Avrami equation and, although previously validated using laser flash analysis and infrared spectroscopy, is not currently transferable to DSC. Application of the model to calorimetric data required long-duration isotherms and a series of data treatments. Once implemented, the square root of time dependence of the secondary process was once again observed. After separation of the secondary process from the primary, a mechanistic n value of 3 was obtained for the primary process. Kinetic parameters obtained from the analysis were used in the model to regenerate the fractional crystallinity curves. Comparison of the model with experimental data generated R² values in excess of 0.995. Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) was used as model polymer due to the prominent secondary crystallisation behaviour that this polymer is known to display.