Phase separation, phase dissolution and crystallization in poly (ε-caprolactone)/poly (styrene-co-acrylonitrile) blends

Abstract

A blend of poly(e-caprolactone) (PCL) and poly(styrene-co-acrylonitrile) (SAN) containing 27.5 wt% of acrylonitrile having the critical composition (80/20 PCL/SAN) was studied. This PCL/SAN blend having a lower critical solution temperature (LCST) phase boundary at 122°C offered an excellent opportunity to investigate, firstly the kinetics of phase separation above LCST (125-180°C), and secondly the kinetics of phase dissolution below LCST (50-115°C). The blend underwent a temperature-jump above LCST where spinodal decomposition (SD) proceeded, yielding a regularly phaseseparated structure (SD structure). Then, it was quenched to the temperatures below LCST when the phase dissolution proceeded. Optical microscopy was used to observe the spinodal decomposition qualitatively while light scattering was used to characterize the phase separation and phase dissolution quantitatively. It was found that during phase dissolution the peak maximum moved towards a smaller angle (wavelength of concentration fluctuations increases) while the peak intensity decreased. This behavior was explained by a model. Also it was found that the fastest phase dissolution kinetics at 80°C, which was characterized by an apparent diffusion coefficient, was about 10 times slower than the kinetics of phase separation at 180°C. Crystallization after various levels of spinodal decomposition was observed by optical microscopy. Order parameter of the lamellae inside the spherulites was evaluated with the help of Hv light scattering. Transmission electron microscopy revealed interesting lamellar structure after spinodal decomposition.