Macromolecules, Vol.44, No.5, 1177-1181, 2011
Further Consideration of Viscoelastic Two Glass Transition Behavior of Nanoparticle-Filled Polymers
Tsagaropoulos and Eisen berg [Macromolecules 1995, 28, 396; Macromolecules 1995, 28, 6067] reported a second loss tangent (tan delta) peak in temperature-dependent viscoelastic data for various un-cross-linked polymers filled with nanometer-sized silica particles. This peak, occurring at temperatures as much as 100 degrees C above the primary tan delta peak (glass-to-rubber softening transition), was ascribed to the glass transition of immobilized chains near the particles. This research is often cited as support for the existence of severely retarded segmental motion of polymer near the surfaces of small particles (glassy polymer shell). We offer a different interpretation of the results from Tsagaropoulos and Eisenberg, reinforced by our recent measurements on particle-filled polybutadiene and consideration of other literature data. Particles restrict the flow of some polymer chains, thus resulting in incomplete terminal relaxation, and partial cross-linking of unfilled polymers produces the same higher temperature tan delta peak. Polymer chains which are adsorbed onto tiller surfaces are immobilized from a flow relaxation (chain diffusion/reptation) standpoint, but segmental relaxation (glass transition) is not substantially altered by small particles as a general rule.