Effect of Mg content on the thermal stability and mechanical behaviour of PLLA/Mg composites processed by hot extrusion.

In the field of bioabsorbable composites for biomedical applications, extrusion has been employed as a method to prepare homogeneous blends of polymeric matrices with bioactive ceramic fillers. In this work, the suitability of processing poly-l-lactic acid/Magnesium (PLLA/Mg) composites by hot extrusion has been assessed by a systematic characterization of PLLA/Mg composites containing different amounts of Mg particles up to 7wt%. The results show that extrusion causes a reduction of almost 20% in the viscosity average molecular weight of PLLA, which further decreases with increasing Mg content. Extrusion gave always rise to a homogeneous distribution of Mg particles within the PLLA matrix. This composite processing was not compromised by the degradation of the polymeric matrix because the processing temperature was always below the onset degradation temperature. In the processing conditions employed in the present work, degradation of the composite slightly increases as more Mg is added up to 5wt%, but is very high at 7wt%. This was also evident from the mechanical behaviour, so that Mg particles improved the stiffness and compression strength of neat PLLA until 5wt% of Mg content, which dropped drastically when the material had 7wt% of Mg. The filler strengthening factor decreases with the increment in Mg content. In order to obtain an optimised contribution of Mg particles, a balance between thermal degradation and mechanical resistance of PLLA must be achieved.

Assessment of mechanical behavior of PLA composites reinforced with Mg micro-particles through depth-sensing indentations analysis.

This work deals with the mechanical characterization by depth-sensing indentation (DSI) of PLLA and PLDA composites reinforced with micro-particles of Mg (up to 15wt%), which is a challenging task since the indented volume must provide information of the bulk composite, i.e. contain enough reinforcement particles. The composites were fabricated by combining hot extrusion and compression moulding. Physico-chemical characterization by TGA and DSC indicates that Mg anticipates the thermal degradation of the polymers but does not compromise their stability during processing. Especial emphasis is devoted to determine the effect of strain rate and Mg content on mechanical behavior, thus important information about the visco-elastic behavior and time-dependent response of the composites is obtained. Relevant for the intended application is that Mg addition increases the elastic modulus and hardness of the polymeric matrices and induces a higher resistance to flow. The elastic modulus obtained by DSI experiments shows good agreement with that obtained by uniaxial compression tests. The results indicate that DSI experiments are a reliable method to calculate the modulus of polymeric composites reinforced with micro-particles. Taking into consideration the mechanical properties results, PLA/Mg composite could be used as substitute for biodegradable monolithic polymeric implants already in the market for orthopedics (freeform meshes, mini plates, screws, pins, …), craniomaxillofacial, or spine.

Antibacterial effect of novel biodegradable and bioresorbable PLDA/Mg composites.

Polylactic acid/Mg composites have been recently proposed for biodegradable osteosynthesis devices because, with regards to the neat polymer, they combine an enhanced biocompatibility and bioactivity with better mechanical properties, particularly creep strength. A question still arises about their bacterial behavior. For this purpose, composites of poly-L-D-lactic acid (PLDA) loaded with 1 and 10 wt.% of Mg microparticles were evaluated using Staphylococcus epidermidis, with special emphasis on the study of bacterial adhesion and biofilm formation. During biofilm formation the bacteria viability of the composites decreased up to 65.3% with respect to PLDA. These antibacterial properties do not compromise the cytocompatibility of the material as the composites enhanced the viability of mesenchymal stem cells and their osteogenic commitment. These findings provide an important added value to the biodegradable and biocompatible PLDA/Mg composites for the manufacture of osteosynthesis devices.

In vitro degradation of biodegradable polylactic acid/magnesium composites: Relevance of Mg particle shape.

Absorbable medical devices must be developed in order to have an appropriate degradation rate in agreement with the healing rate of bone in the implantation site. In this work, biodegradable composites formed by a polylactic acid matrix reinforced with 10%wt. magnesium microparticles were processed and their in vitro degradation investigated during 28 days. A joint analysis of the amount of H2 released, the changes in pH in buffered (PBS) and non-buffered media (distilled water), the variations in mass, microstructure and the mechanical performance of the specimens was developed. The main aim was to elucidate the relevance of Mg particles shape on tailoring the degradation kinetics of these novel composites. The results show that the shape of the Mg reinforcing particles plays a crucial role in the degradation rate of PLA/Mg composites, with spherical particles promoting a lower degradation rate than irregular particles. This fact is only partially due to the smaller surface area to volume ratio of the spherical particles. Irregular particles promote a faster formation of cracks and, therefore, an increasingly faster degradation of the polymeric matrix. In every case, the amount of H2 released by the composites was well below that released by monolithic Mg. The pH of PBS during degradation remained always within 7.2 and 7.4. PLA/Mg reinforced with spherical particles retains more than 90% of its mechanical properties after 7 days of immersion and more than 60% after 28 days. STATEMENT OF SIGNIFICANCE: The increasing demand for temporary orthopaedic implants is the driving force to seek new strategies to decrease costs and simultaneously improve patients comfort as well as simplify surgical procedures. Resorbable medical devices must be developed in order to have an appropriate degradation rate in agreement with the healing rate of bone. We are presenting for the first time results of the degradation kinetics of a new material based on polylactic acid reinforced with 10%wt. Mg microparticles. This work analyzes the relevance of Mg particle shape (irregular and spherical) on tailoring the degradation behaviour of these composites. Conclusions withdrawn from this study help to customize bioabsorbable materials in order to meet the requirements for a specific application and patient.