Thermal and Rheological Analysis of Polystyrene-Grafted Silica Nanocomposites

Two matrix-free polystyrene-grafted silica nanocomposite samples with graft chain lengths of 35 and 112 kg/mol are characterized by calorimetry and rheometry, and results are compared to neat polystyrenes of comparable molecular weights. The glass transition temperature T_g of the nanocomposites is found to be approximately 1 to 2 K higher than that of the neat materials, whereas the absolute heat capacity is approximately 4-7% lower in the glassy and liquid states. The step change in heat capacity ΔC_p at T_g is 15% lower for the nanocomposites, consistent with an immobilized glassy layer of approximately 2 nm. The linear viscoelastic behavior of the nanocomposite samples differs significantly compared to their neat analogs in several ways: first, the G′ versus ω curves shift toward lower frequencies by approximately one decade due to the increase in the glass transition temperature; second, terminal flow behavior is absent; third, the rubbery plateau moduli (G_N°) decreases by 7% for the 35 kg/mol grafted particles and increases by approximately two and a half-fold for the 112 kg/mol grafted particles; and fourth, the glassy modulus increases approximately 4% consistent with hydrodynamic reinforcement. On the other hand, the magnitude of the rubbery modulus is attributed to two effects, hydrodynamic reinforcement and a change in the effective entanglement density, which is governed by corona interpenetration coupled with the silica particles acting as physical entanglement points.