Molar mass dependent growth of poly(epsilon-caprolactone) crystals in Langmuir films

Poly(epsilon-caprolactone) (PCL) samples with number average molar masses (Mn) ranging from 3.5 to 36 kg.mol-1 exhibit molar mass dependent nucleation and growth of crystals, crystal morphologies, and melting properties at a temperature of 22.5 degrees C in Langmuir films at the air/water (A/W) interface. At surface area per monomer, A, greater than approximately 0.37 nm2.monomer-1, surface pressure, Pi, and surface elasticity exhibit molar mass independent behavior that is consistent with a semidilute PCL monolayer. In this regime, the scaling exponent indicates that the A/W interface is a good solvent for the liquid-expanded PCL monolayers. Pi-A isotherms show molar mass dependent behavior in the vicinity of the collapse transition, i.e., the supersaturated monolayer state, corresponding to the onset of the nucleation of crystals. Molar mass dependent morphological features for PCL crystals and their subsequent crystal melting are studied by in situ Brewster angle microscopy during hysteresis experiments. The competition between lower segmental mobility and a greater degree of undercooling with increasing molar mass produces a maximum average growth rate at intermediate molar mass. This behavior is analogous to spherulitic growth in bulk PCL melts. The plateau regions in the expansion isotherms represent the melting process, where the polymer chains continuously return to the monolayer state. The magnitude of Pi for the plateau during expansion decreases with increasing molar mass, indicating that the melting process is strongly molar mass dependent.