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Here, nanocomposites of high-molecular-weight polyethylene (HMWPE) and HMWPE-UHMWPE (80/20 wt.%) containing a low amount of multilayer graphene oxide (mGO) (≤0.1 wt.%) were produced via twin-screw extrusion to produce materials with a higher tribological performance than UHMWPE. Due to the high viscosity of both polymers, the nanocomposites presented a significant concentration of agglomerates. However, the mechanical (tensile) and tribological (volumetric loss) performances of the nanocomposites were superior to those of UHMWPE. The morphology of the nanocomposites was investigated using differential scanning calorimetry (DSC), microtomography, and transmission electron microscopy (TEM). The explanation for these results is based on the superlubricity phenomenon of mGO agglomerates. It was also shown that the well-exfoliated mGO also contained in the nanocomposite was of fundamental importance as a mechanical reinforcement for the polymer. Even with a high concentration of agglomerates, the nanocomposites displayed tribological properties superior to UHMWPE’s (wear resistance up to 27% higher and friction coefficient up to 57% lower). Therefore, this manuscript brings a new exception to the rule, showing that agglomerates can act in a beneficial way to the mechanical properties of polymers, as long as the superlubricity phenomenon is present in the agglomerates contained in the polymer.

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