Determination of Crystalline Content Gradients in Cold-Drawn Poly-L-Lactic Acid Films by DSC

Poly-L-lactic acid (PLLA) is a semi-crystalline, optically active, biodegradable, and biocompatible polymer that has been utilized extensively in biomedical applications as an implantable artificial cell scaffold material. In its crystalline form, PLLA is piezoelectric and it has been implicated in the enhancement of electromechanically induced osteogenesis in vivo. In its amorphous state, however, PLLA does not exhibit piezoelectricity. By uniaxially cold-drawing the polymer, PLLA can be endowed with varying degrees of piezoelectricity. It is important to understand the crystalline architecture of drawn PLLA so that the osteogenic potential imparted by piezoelectricity, if any, can be differentiated from the effects of sample crystallinity. In our work we investigate the induced crystallinity for samples of drawn PLLA at draw ratios between 1.0 and 5.5 by differential scanning calorimetry (DSC). As long-range molecular ordering occurs along the draw axis, we observe an increase in the average percent crystallinity up to a draw ratio of 5.0 and a slight decrease at a draw ratio of 5.5. More importantly, we observe significant heterogeneity in the crystalline content along the draw axis of standard dumbbells cut from PLLA and cold-drawn to representative draw ratios of 2.5 and 4.0. On average, the highest percent crystallinity occurs nearest the dumbbell center, but the maximum crystallinity is independent of draw ratio. Therefore, the draw ratio should not be considered a semi-quantitative estimate of localized PLLA crystallinity and point-to-point analysis of crystallinity in PLLA samples is required for constructing scaffolds with enhanced cell growth properties