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Incorporation of rigid nanoparticles is the most effective means of improving polymer properties. Montmorillonite (MMT) and multi-walled carbon nanotubes (MWCNTs) are legendary in this field for their individual exceptional properties. A synergistic phenomenon is induced between these two particles when they are simultaneously incorporated into polymers. At a definite nanofillers concentration, called the percolation threshold, there is a sudden change in nanocomposite properties due to the formation of a 3D-structured network of the nanoparticles within the matrix. In this work, the properties of poly(lactic acid) (PLA) nanocomposites filled with different fractions of MMT/MWCNTs hybrid (0.5–2.0 wt%) were analyzed. In particular, the percolation threshold of the MMT/MWCNTs hybrid was uniquely identified by differential scanning calorimetry, thermogravimetric analysis and dynamic mechanical thermal analysis. The structural studies by X-ray diffraction and Fourier-transform infrared spectroscopy were also associated with the percolation threshold of MMT/MWCNTs in PLA. At 1.0 wt% MMT/MWCNTs concentration, the complete exfoliation of the particles was maintained, and the thermal characteristics such as glass transition, crystallization and melting temperatures reached their plateau at this hybrid concentration. Moreover, the thermal degradation and viscoelastic parameters showed their peak values at this critical point, which is correlated with the formation of the percolation threshold within the matrix. The morphological studies confirmed the homogeneous dispersion of MMT/MWCNTs in PLA up to a concentration of 1.0 wt%. At 2.0 wt% MMT/MWCNTs, few aggregations occurred in the PLA-based composite, confirming that the percolation threshold was formed at a lower concentration of MMT/MWCNTs nanoparticles.

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