Effect of stereocomplex formation in d-lactide-containing plla on thermal behaviors and mechanical property changes using the ageing degradation test

Introduction: The formation of a stereocomplex between PLLA and PDLA has been studied intensively because it increases the mechanical performance and thermal/hydrolytic resistance of polylactide-based materials; however, few studies have investigated the stereocomplex formation between PLLA and the (D-lactide)-containing PLLA copolymer. To investigate the effect of the D-lactide content of PLLA on the thermal behaviors and mechanical properties, (5D/95L) polylactide [(5D/95L)PLA], which contains a molar ratio of 5% of the D-form and 95% of the L-form of the monomer, and (15D/85L) polylactide [(15D/85L)PLA], which contains a molar ratio of 15% of the D-form and 85% of the L-form of the monomer, were used in a series of specimens. For the hydrolytic degradation test, the specimens were placed in 20-mL vials, which were filled with phosphate-buffered solution; the vials were allowed to stand at 57°C for 91 days in accordance with the ASTM F1635-95 (2000) standard test method for in vitro studies. The mechanical properties, thermal properties and crystallization behaviors were investigated using DSC and MTS, respectively. Results: The initial bending strength of the (5D/95L)PLA and (15D/85L)PLA were 35.4 and 31.1 N, respectively. After 1 week, the binding strength of the (5D/95L)PLA increased by 9.8%, and the binding strength of the (15D/85L)PLA decreased by 26%. In addition, the DSC curve of the (5D/95L)PLA demonstrated a higher melting temperature in the 1st week, and this Tc was observed in the DSC curve of the (5D/95L)PLA only during this time. The DSC curve of the (15D/85L)PLA was irregular. Discussion & Conclusions: In the (5D/95L)PLA, the recrystallization that occurred during the hydrolysis process was confirmed by the Tc and the increase in the bending strength. The stereocomplex crystallites may be formed in the (15D/85L)PLA during the degradation process. Because of the increase in the D-form monomer, the stereocomplexes were generated more easily and acted as nucleation sites. The PLLA crystal near the stereocomplex crystallites exhibited an incomplete structure, which led to a faster decrease in the bending strength. The low D-lactide content in the matrix of the PLLA did not form a stereocomplex crystallite because the surface area was not large enough to act as a nucleation site. However, the higher D-lactide-containing fraction formed a large stereocomplex crystallite. The (5D/95L)PLA demonstrated better thermal/hydrolytic resistance and mechanical stability than the (15D/85L)PLA.