Isothermal crystallization kinetics of silk fibroin fiber‐reinforced poly(ε‐caprolactone) biocomposites

BACKGROUND: Poly(ε‐caprolactone) (PCL) has attracted great attention due to its wide applications for pharmaceutical controlled released systems and implanted polymer devices. In this study, silk fibroin fiber (SF) obtained from degumming treatment of silk was used to prepare novel reinforced PCL biocomposites. The isothermal crystallization behavior of these composites was investigated using differential scanning calorimetry measurements. RESULTS: With a decrease of isothermal crystallization temperature (T_c) and an increase of fiber filler, the crystallization time of the SF/PCL composites becomes shorter, the crystallization rate constant (K) increases and the Avrami exponent (n) gradually decreases (being between 1 and 2). The crystallization of PCL and SF/PCL composites occurs in the same regime. With the gradual addition of fiber, lateral surface free energy (σ) is nearly unchanged, but fold surface free energy (σ_e) decreases. CONCLUSION: Heterogeneous nucleation is dominant and different growth morphologies coexist during the isothermal crystallization process of the SF/PCL hybrid systems. Although the introduction of SF obviously increases the overall crystallization rate of PCL, the growth rate constant and nucleation constant of PCL are reduced because of the confinement effect of fiber network structures on the molecular mobility of polymer molecular chains. Copyright © 2009 Society of Chemical Industry