Modulating Barrier Properties of Stereocomplex Polylactide: The Polymorphism Mechanism and Its Relationship with Rigid Amorphous Fraction

The barrier properties of semicrystalline polymers are crucial for their performance and their use as packaging materials. This work uncovers the mechanism of polymorphism modification (α, α' and stereocomplex-crystals) and its combined effect on the oxygen and water vapor barrier properties of semicrystalline stereocomplex polylactide (SCPLA). A polymorphic selective filler-type nucleator was employed to eliminate the temperature effect on the development of polymorphism and rigid amorphous fraction (RAF), allowing correlations of barrier properties with different crystal forms and RAF combinations under the same amorphous composition (SCPLA). The oxygen and water vapor barrier performances strongly correlated with crystallinity and crystal form but were not monotonically related to the RAF quantity. The study proposes that the chain conformation of intermediate phases between the crystalline and amorphous phases differs with the associated crystal forms, thereby leading to different RAF "qualities" and contributing to different gas diffusion and solubility coefficients of the amorphous regions. RAF's per unit excess free volume may be varied with crystal forms, for instance: α' ≫ SC > α. Therefore, SCPLA with α' crystals exhibited high oxygen and water vapor permeabilities. Those with high SC and α crystals showed similar barrier behaviors governed by Henry's law dissolution and followed a linear "two-phase" relationship with total crystallinity.