Flow-Induced Precursor Formation of Poly(l-lactic acid) under Pressure

For the first time, the influences of two inevitable processing fields (pressure and flow fields) on the crystallization of a semirigid molecular chain polymer, that is, poly(l-lactic acid) (PLLA), were explored using a homemade pressuring and shearing device. The results reveal that the shear rate facilitated the generation of precursor because it induced oriented segment formation. It was found that the most sensitive shear temperature for the generation of PLLA precursor under 100 MPa was 180 °C. When the shear temperature was higher (e.g., 190 °C), the relaxation of shear-induced oriented segments was too quick to induce the generation of PLLA precursor. Oppositely, at a lower shear temperature (170 °C), the oriented segments were hard to relax within the whole shear rate range (3.1-31.4 s^-1). Annealing treatment was infaust to the PLLA precursor formation because it promoted the relaxation of oriented segments. Different from the shear and annealing, pressure played a more complicated role in the formation of PLLA precursor. Pressure decreased the free volume between PLLA molecular chains and meantime increased the supercooling of PLLA melt. In addition, PLLA chains tended to form locally oriented segment bundles to adapt to the pressurized state, which facilitated the formation of PLLA precursor and the following crystallization process. These two factors lowered the movability of PLLA chains and suppressed the relaxation of chain, so shear-induced orientation facilitated PLLA precursor formation under pressure. In that case, pressure and shear flow showed a synergetic promoting effect on the generation of PLLA precursor and the following crystallization process. These meaningful results could be helpful for comprehending the relationship between crystallization conditions and the crystallization behavior of PLLA and thus would provide guidance to fabricating the final products through controlling the crystallization process of PLLA.