Constrained amorphous interphase in plasticized poly(lactic acid): Composition and tensile elastic modulus estimation

The study investigates the distribution of the plasticizers acetyl triethyl citrate (ATEC) and acetyl tributyl citrate (ATBC) in the mobile amorphous (MAF) and rigid amorphous (RAF) fractions of semi-crystalline plasticized poly(lactic acid) (PLA) containing 5 wt% of plasticizer. During crystallization, the ATEC and ATBC concentration in the MAF increases from 5 to about 8 wt%. At the end of crystallization, the plasticizers concentration in the RAF is lower than that in the MAF. The progressive decrease of the ATEC and ATBC concentration in the RAF region could be linked to the growth of subsidiary lamellae in more restricted amorphous areas. The study also introduces an estimation of the tensile elastic modulus of the RAF (ERAF) in semi-crystalline pure and plasticized PLA containing ?-crystals. The mechanical model with crystalline lamellae perpendicular to the stress direction turned out to be the most appropriate arrangement to represent the morphological organization in PLA samples prepared by injection-moulding processing at high pressure. The mathematical procedure led to a crystal elastic modulus (EC) of the ?-phase in excellent agreement with the theoretical value reported in the literature (EC = 14 GPa), and to an ERAF value around 5.5 GPa, for both pure and plasticized PLA, thus suggesting that both ATEC and ATBC do not exert plasticizing action on the RAF.