A comparative study on Poly(ε-caprolactone) film degradation at extreme pH values

The present paper studies the effect of pH on hydrolytic degradation of Poly(ε-caprolactone) (PCL) Degradation of the films was performed at 37 °C in 2.5 M NaOH solution (pH 13) and 2.5 M HCl solution (pH 1). Weight loss, degree of swelling, molecular weight, and calorimetric and mechanical properties were obtained as a function of degradation time. Morphological changes in the samples were carefully studied through electron microscopy. At the start of the process the degradation rate of PCL films at pH 13 was faster than at pH 1. In the latter case, there was an induction period of around 300 h with no changes in weight loss or swelling rate, but there were drastic changes in molecular weight and crystallinity. The changes in some properties throughout the degradation period, such as crystallinity, molecular weight and Young's modulus were lower in degradations at higher pH, highlighting differences in the degradation mechanism of alkaline and acid hydrolysis. Along with visual inspection of the degraded samples, this suggests a surface degradation at pH 13, whereas bulk degradation may occur at pH 1.