Abstract
ABSTRACTWe present a simulation study showing the effect of bidispersity in matrix homopolymer length on the wetting/dewetting of homopolymer‐grafted nanoparticles and the morphology of polymer nanocomposites where the graft and matrix polymer chemistries are identical. In a bidisperse matrix with equal number of short and long chains and average matrix length greater than the monodisperse graft length, the densely grafted polymer layer is preferentially wet by the short chains and relatively dewet by the long chains. This is driven by a larger gain in entropy of mixing between graft and matrix for short matrix chains than long matrix chains. Despite the preferential wetting of the short and dewetting of long chains, matrix length bidispersity does not significantly change the overall wetting of the grafted layer. Unlike graft length bidispersity that significantly improves particle dispersion, matrix length bidispersity slightly increases particle aggregation in the polymer matrix. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014, 52, 1661–1668
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