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Nanocomposites represent a new prospective branch in the huge field of polymer materials science and technology. It has been shown that an overall enhancement of properties of polymers can be achieved under certain conditions by the addition of nanoparticles. To examine the influence of microstructure on the tribological performance of nanocomposites, different ways of compounding were used in this study. It was found that the friction and wear behavior of polymeric nanocomposites under sliding environment was rather sensitive to the dispersion states of the nanoparticles. When the microstructural homogeneity of the nanocomposites was improved, their wear resistance could be increased significantly. The present work demonstrates the importance of TiO2‐nanoparticles dispersion in an epoxy resin matrix, on the materials’ tribological properties, when sliding against a smooth steel counterpart.

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