Abstract
Poly(methyl methacrylate)s (PMMA) containing both tethered and untethered polyhedral oligomeric silsesquioxanes (POSS) were examined through the use of wide-angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), and rheological characterization. The presence of tethered-POSS in entangled copolymers leads to a decrease in the plateau modulus ( ) when compared with PMMA homopolymer. Two untethered-POSS fillers, cyclohexyl-POSS and isobutyl-POSS, were blended with PMMA homopolymer. Both DSC and rheological results suggest a regime at low untethered-POSS loadings (φ ≤ 0.05) in PMMA in which much of the POSS filler resides in the matrix in a nanoscopically dispersed state. This well-dispersed POSS decreases the zero-shear-rate viscosity (η0). Above this regime, an apparent solubility limit is reached, and beyond this point additional untethered-POSS aggregates into crystallites in the PMMA matrix. These crystallites cause both the viscosity and the plateau modulus to increase in a way consist...
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