Heterogeneous nucleation and self-nucleation of poly(p-dioxanone)

The changes in nucleation behaviour upon addition of Boron Nitride (BN), Talc and Hydroxyapatite (HA) to poly(p-dioxanone) (PPDX) were monitored by DSC and Polarised Optical Microscopy (PM). Self-nucleation DSC studies evidenced the existence of the usual three self-nucleation domains depending on the self-nucleation temperature (T s) employed. By far the best nucleation agents for PPDX were its own self-nuclei and this result was independent of the presence or absence of any of the other nucleating agents employed; once Domain II was reached, self-nucleation dominated the nucleation process. BN and Talc were able to nucleate PPDX, thereby increasing its nucleation density, its dynamic crystallisation temperature upon cooling from the melt (T c) and its enthalpy of crystallisation (ΔH c). BN was a better nucleating agent than talc. HA on the other hand caused an “antinucleation” effect on PPDX characterised by a decrease in its nucleation density, a decrease in its T c and in ΔH c. Isothermally crystallised PPDX exhibited large banded spherulites whose morphology changed as a function of crystallisation temperature from single banded structures with a very clear Maltese cross to double banded spherulites. PPDX also shows a change in growth regime upon increasing crystallisation temperature (from Regime III to Regime II) according to the kinetic interpretation of growth rate data. BN did not cause any significant modification of the spherulitic growth kinetics (in Regime II) except for a small decrease in surface free energy of PPDX crystals (σe). On the other hand HA was found to increase the spherulitic growth rate and the overall crystallisation rate of PPDX, this increase was caused by a degradation process experienced by the polymer during the treatments involved in isothermal crystallisation that was only present in the samples with HA. It is postulated that the interaction between the phosphate groups on the surface of HA and the ester groups of PPDX are responsible for both the antinucleation effect and the catalysis of the hydrolytic degradation of PPDX.