Specific Impact of the Layered Nanomodifiers—Graphene Nanoplates, and Na+ Montmorillonite on Thermal Degradation of Polylactic Acid: Mechanism and Kinetics

The aim of this study is to investigate the impact of layered nanomodifiers with distinct chemical structure and morphology, namely graphene nanoplates (GnP) and sodium montmorillonite (Na-MMT), on thermal degradation of polylactic acid (PLA). The exploration was performed with thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and pyrolytic gas chromatography–mass spectrometry (PyGCMS). The findings revealed a catalytic effect of Na-MMT on PLA thermal destabilization, manifested in accelerated degradation and the notable change in the composition of pyrolysis products. In contrast, the incorporation of graphene nanoplates into the PLA matrix induced a “barrier effect”: it imposed diffusion limitations on the emission of volatile degradation products during pyrolysis, which enhanced the thermal stability of the PLA/GnP composite and led to quantitative alterations in the distribution of major pyrolysis products. To elucidate the underlying degradation pathways, authors proposed a model kinetic analysis of thermal degradation for both PLA/GnP and PLA/Na-MMT composites. The analysis clearly distinguished the mechanistic differences between the two systems: while Na-MMT promotes catalytic decomposition, GnP primarily acts as the physical barrier retarding mass transport and delaying the thermal degradation development. Good alignment of theoretical model–kinetic predictions with Pyrolysis–GC/MS observations confirms the robustness of the suggested kinetic modeling method.