Crystallization kinetics of PCL and PCL–glass composites for additive manufacturing

Abstract

The non-isothermal crystallization kinetics of polycaprolactone (PCL) and PCL–glass composites, used in fused filament fabrication (FFF), was investigated. Films of PCL and PCL reinforced with powders of a bioactive glass, from the CaO·P2O5·MgO·SiO2 system, were prepared by solvent casting process. Crystal structure of the samples was examined by X-ray diffraction (XRD), and thermal properties were assessed by differential scanning calorimetry (DSC), at different cooling rates (5, 10, 15 and 20 °C min−1). The DSC curves of non-isothermal crystallization showed a significant dependence of crystallinity (Xc) on the cooling rate. The relevant crystallization kinetic parameters were determined from DSC traces applying a combination of Avrami and Ozawa methods (Mo’s method), Jeziorny method and Friedman method. It was observed that the presence of inorganic particles within the polymeric matrix clearly influenced the composite crystallization. The addition of glass particles allowed a decrease in Xc and accelerated the PCL crystallization rate. The slower cooling rates tested proved to be suitable for the biofabrication of PCL–glass composites by FFF techniques.