Macroscopic volume as well as capacitive dilatometry (CD) measurements have been performed on polystyrene/silica nanocomposites during the course of physical aging below the glass transition temperature (Tg). Our results show that the macroscopic volume recovery during physical aging is not affected by the presence of nanofillers, whereas the CD measurements, delivering also information on the polymer matrix density, show acceleration of the recovery with increasing the silica content. Hence, the main outcome of the present work is that the evolution of macroscopic and matrix densities are markedly different in polymer nanocomposites. We interpret these results invoking an equilibration mechanism based on volume holes diffusion. According to this model, excess free volume migration at the polymer/filler interface only modifies the matrix density, thereby explaining the faster recovery detected by CD measurements in comparison to the macroscopic volume one. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys., 2013
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