Comparison of the hydrolytic degradation and deformation properties of a PLLA-lauric acid based family of biomaterials.

Addition of lauric acid to PLLA results in a significantly increased rate of hydrolytic degradation, with the time-to-loss of tensile strength directly related to the concentration of lauric acid. In this study, the hydrolytic degradation profiles of four materials were studied: amorphous PLLA, amorphous PLLA containing 1.8 wt % lauric acid, amorphous PLLA containing 4.5 wt % lauric acid, and pre-crystallized PLLA containing 1.8 wt % lauric acid. Hydrolytic degradation was monitored through mass profiles, molecular weight profiles, crystallinity and the development of mechanical properties and deformation mechanisms (through simultaneous small-angle X-ray scattering and tensile testing), and a "phase diagram" of properties suggested. The key factor in determining the development of properties was found to be the time at which crystallization occurred in relation to the loss of molecular weight, with the two factors most affecting this being the lauric acid content and the pre-degradation annealing treatment.

The effect of crystallinity on the deformation mechanism and bulk mechanical properties of PLLA.

Poly (l-lactide) is a widely studied biomaterial, currently approved for use in a range of medical devices, however, most in vitro studies have so far focussed upon either the bulk properties during degradation and/or deformation, or on the microstructure of the unloaded material during degradation. This study aimed to combine these approaches through the technique of simultaneous small-angle X-ray scattering and tensile testing at various stages of degradation up to 8 months, on material with a range of induced microstructures. Results showed that the amorphous material deformed by crazing in the dry, wet and degraded states, however, the mechanism by which the craze developed changed significantly on hydration. Despite this difference, there was little change in the bulk mechanical properties. Crystalline materials deformed through crystal-mediated deformation, with contributions from both cavitation and fibrillated shear, but surprisingly, differences in the length scales within the spherulitic structure caused by annealing at different temperatures had very little effect on the mechanism of deformation, though differences were seen in the bulk properties. Furthermore, hydration had little effect on the crystalline materials, though degradation over 8 months resulted in loss of mechanical properties for samples produced at higher annealing temperatures. In conclusion, the introduction of crystallinity had a huge effect on both bulk and microscopic properties of PLLA, but the spherulitic structure of the crystalline material affected the bulk properties significantly more than it did the micromechanism of deformation.

A degradation study of PLLA containing lauric acid.

Addition of lauric acid to poly (L-lactide) (PLLA) has resulted in a new family of enhanced degradation biomaterials. Presented is PLLA4.5 (PLLA containing 4.5 wt% lauric acid), the fastest degrading of the family. Degradation was studied via mass changes, gel-permeation chromatography, wide- and small-angle X-ray scattering (WAXS and SAXS), simultaneous SAXS and tensile testing, and visual observation. The undegraded PLLA4.5 deformed by crazing, recognisable from the characteristic shape of the SAXS pattern. As water up-take and degradation proceeded, samples crystallised, decreasing the SAXS long period, until by 4 days the deformation mechanism had become that of crystal-mediated deformation. This resulted in a 'peanut-lemon'-shaped SAXS pattern, interpreted in terms of cavitation and fibrillated shear. Further degradation up to 12 days resulted in the same deformation mechanism at different sample displacements, with samples failing earlier during tensile testing until a ductile-brittle transition occurred. At 30-40 days water up-take and mass-loss increased significantly and global whitening of samples occurred, while the crystallinity and long period stabilised. Complete degradation had not occurred by the end of the study at 73 days. Through an understanding of how the changes in morphology during degradation affect the micromechanisms of deformation, it may be possible to design microstructures to give a tailored evolution of mechanical response in the body.