Nanocomposites were prepared via melt blending, based on organically modified clays (OC), carbon nanotubes (CNT), and graphitic nanofillers made by a few layers of graphene (nanoG). In particular, nanocomposites based on a hybrid filler system, with a nanostructured filler such as carbon black (CB), are examined. It is shown that low crystalline order in the interlayer space of a layered nanofiller (such as OC and nanoG) leads to easier delamination. Nanofillers give rise to filler networking at low concentration, particularly in the presence of CB. Hybrid filler systems lead to nanocomposites' having initial moduli that are much higher than those calculated through the sum of the initial modulus of composites containing either only CB or only the nanofiller. Nanofillers enhance the matrix modulus by a multiplication factor that depends only on the nanofiller type and content, regardless of whether the matrix is a neat or a CB-filled polymer. Furthermore, the filler–polymer interfacial area is shown to be a parameter able to correlate the mechanical behavior of both nano-CNT and nanostructured (CB) fillers. By plotting values of the composite initial modulus versus the filler–polymer interfacial area, points due to CB, CNT, and the hybrid CB-CNT system lie on the same curve.
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