Morphology, molecular interactions and H₂O diffusion in a poly(lactic-acid)/graphene composite: A vibrational spectroscopy study

A composite system made of poly(l-lactic acid) (PLLA) and graphene nanoplatelets (GNP) was investigated by Raman and FTIR spectroscopy. Two compositions were prepared and characterized in comparison to the pristine polymer: they contained, respectively, 0.25 and 0.75 wt% of the nanofiller. The study was focused on the morphological properties of the system, and, in particular, on the level of dispersion and the homogeneity obtainable with the adopted preparation protocol. Furthermore, the possible molecular interactions taking place between the nanofiller and the polymer matrix were considered. Both the above issues were investigated by confocal Raman spectroscopy, with the aid of first-principle calculations to strengthen the spectral interpretation. Finally, the effect of the nanofiller on water diffusion was investigated by time-resolved FTIR spectroscopy, which provided accurate equilibrium and kinetic data, as well as molecular level information on the penetrant-to-substrate interactions. It was found that, for a 0.25 wt% composition, the adopted preparation protocol allowed us to achieve a dispersion at the level of single nanoplatelets, while for a 0.75 wt% composition, the GNP's aggregate into a co-continuous phase. PLLA/GNP interactions were detected by Raman spectroscopy, producing a detectable perturbation of the PLLA conformational equilibrium. Both the diffusivities and the equilibrium water uptake were found to decrease significantly by increasing the filler content.