Polymer architecture effect on rheology and segmental dynamics in poly (methyl methacrylate)-silica nanocomposite melts.

Architecturally different polymer chains lead to fundamentally different rheological responses and internal dynamics, which can be utilized to rationalize advanced thermoplastic nanocomposites with tunable mechanical behavior. In this work, three model poly (methyl methacrylate) (PMMA) polymers with linear, bottlebrush, and star architectures with the same total molar mass were investigated in their neat form, and nanocomposites with well-dispersed silica nanoparticles using rheology and broadband dielectric spectroscopy (BDS). The master curves of the dynamic moduli obtained by time-temperature superposition (TTS) over the entire range from the Rouse regime to the terminal flow and a sequence of significantly different relaxation modes were observed for the samples with linear and branch chains. While linear chains form an entangled polymer network, the branched bottlebrush, and star chains show a viscoelastic response with no sign of rubbery entanglement plateau and a weak arm relaxation regime between Rouse and terminal flow, akin to other branched polymers. Moreover, branched chains showed a higher fragility index (m = 3.46 for the bottlebrush and 5.36 for the star) compared to linear chains (m = 3.29) due to dynamical heterogeneities induced by arm relaxation. The addition of nanoparticles affects only the terminal relaxation regime, where the whole chain motion is hindered by the attractive nanoparticles. The dynamics of the polymer segment were investigated by performing broadband dielectric spectroscopy (BDS) at a frequency range from 10 Hz to 10 Hz. The results revealed more than 10 times slower segmental relaxation for the star homopolymers and a slowdown in the α-relaxation process for all three architectures in their composite form. The dynamical slowdown in the composites is temperature dependent and more pronounced at low temperatures (leading to approximately equal to 80 times slower dynamics for nanocomposite with bottlebrush PMMA at 150 °C) due to prolonged relaxation of the interfacial polymer compared to the matrix chains. The results from this study have practical applications in fields such as gas separation and polymeric electrolyte membranes, where simultaneous improvement of segmental mobility and mechanical moduli is highly desired.