Physical and mechanical degradation behaviour of semi-crystalline PLLA for bioresorbable stent applications

This study presents a systematic evaluation of the physical, thermal and mechanical performance of medical-grade semi-crystalline PLLA undergoing thermally-accelerated degradation. Samples were immersed in phosphate-buffered saline solution at 50°C for 112 days and mass loss, molecular weight, thermal properties, degree of crystallinity, FTIR and Raman spectra, tensile elastic modulus, yield stress and failure stress/strain were evaluated at consecutive time points. Samples showed a consistent reduction in molecular weight and melting temperature, a consistent increase in percent crystallinity and limited changes in glass transition temperature and mass loss. At day 49, a drastic reduction in tensile failure strain was observed, despite the fact that elastic modulus, yield and tensile strength of samples were maintained. Brittleness increase was followed by rapid increase in degradation rate. Beyond day 70, samples became too brittle to test indicating substantial deterioration of their load-bearing capacity. This study also presents a computational micromechanics framework that demonstrates that the elastic modulus of a semi-crystalline polymer undergoing degradation can be maintained, despite a reducing molecular weight through compensatory increases in percent crystallinity. This study presents novel insight into the relationship between physical properties and mechanical performance of medical-grade PLLA during degradation and could have important implications for design and development of bioresorbable stents for vascular applications.