Physical aging and glass transition of hairy nanoparticle assemblies

Matrix free assemblies of polymer‐grafted, “hairy” nanoparticles (aHNP) exhibit novel morphology, dielectric, and mechanical properties, as well as providing means to overcome dispersion challenges ubiquitous to conventional polymer‐inorganic nanocomposite blends. Physical aging of the amorphous polymer glass between the close‐packed nanoparticles (NPs) will dominate long‐term stability; however, the energetics of volume recovery within the aHNPs is unknown. Herein, we compare glass transition temperature (Tg) and enthalpy recovery of aHNPs to NP‐polymer blends, across different nano‐silica loadings (0–50 v/v%) and canopy architecture of polystyrene (PS) grafted silica. For aHNPs, the grafting of PS to silica imposes an additional design constraint between silica volume fraction, graft density, and graft molecular weight. At low and intermediate silica volume fraction, the Tg of blended nanocomposites is independent of silica content, reflecting a neutral polymer‐NP interface. For aHNPs, the Tg decreases with silica content, implying that chain tethering decreases local segment density more than the effect of molecular weight or polymer‐NP interactions. Additionally, the Tg of the aHNPs is higher than a linear matrix of comparable molecular weight, implying a complementary effect to local segment density that constrains cooperativity. In contrast, enthalpy recovery rate in the blend or aHNP glass is retarded comparably. In addition, a cross‐over temperature, Tₓ, emerges deep within the glass where the enthalpy recovery process of all nanocomposites becomes similar to linear unfilled matrices. Differences between structural recovery in aHNP and blended nanocomposites occur only at the highest silica loadings (∼ 50 v/v%), where enthalpy recovery for aHNPs is substantially suppressed relative to the blended counterparts. The absence of physical aging at these loadings is independent of brush architecture (graft density or molecular weight of tethered chains) and indicates that the impact of chain tethering on effective bulk structural relaxation starts to appear at particle‐particle surface separations on the order of the Kuhn length. Overall, these observations can be understood within the context of how three separate structural characteristics impact local segment density and relaxation processes: the dimension and architecture of the tethered polymer chains, the separation between NP surfaces, and the confinement imposed by chain tethering and space filling within the aHNP. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 319–330