Structure Versus Properties Relationship of Poly(lactic acid). I. Effect of Crystallinity on Barrier Properties

Poly(lactic acid) is at present the most promising and commercially available bio-based and biocompostable (bio)plastic. The properties of PLA, however, are rather poor, notably its low glass transition temperature T-g of similar to 55 degrees C, its intrinsic low crystallization rate and the limited barrier properties with respect to water, oxygen and carbon dioxide in comparison with to oil-based counterparts, notably polyesters (PET). In this manuscript we address the question of what could ultimately be achieved in terms of barrier properties when PLA is crystallized fully. In fact, this question is rather academic in view of the long crystallization/annealing times needed to obtain maximum crystallinity but serves the purpose of better understanding current limits and notably a better understanding of the role of crystallinity on the barrier properties. A correlation is made between crystallization, various morphological parameters and the barrier properties of PLA. Crystallization of PLA causes a decrease of the oxygen permeability, but not in linear proportion with the decrease in amorphous volume. We explain this in terms of influence of the space filling and the inner crystalline structure on gas transport properties. Furthermore we suggest that the presence of a rigid amorphous fraction with lower density can have strong impact on PLA gas permeability, in particular on the gas solubility coefficient of PLA. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2247-2258, 2009