RESUMO
We present a systematic study of the structural dynamics in bulk entropic polymer nanocomposites (PNCs) with deuterated-polymer-grafted nanoparticles (DPGNPs) using quasi-elastic neutron scattering (QENS). We observe that the wave-vector-dependent relaxation dynamics depend on the entropic parameter f as well as the length scale being probed. The entropic parameter can be defined in terms of the grafted-to-matrix polymer molecular weight ratio and controls the extent of matrix chain penetration into the graft. Dynamical cross-over from Gaussian to non-Gaussian behavior at the wave vector Qc, which depends on temperature and f, was observed. Further insight into the underlying microscopic mechanism responsible for the observed behavior revealed that when interpreted using a jump-diffusion model, in addition to the speeding-up in local chain dynamics, the elementary distance over which sections of the chain hop is strongly dependent on f. Interestingly, we also observe dynamic heterogeneity (DH) in the studied systems, characterized by the non-Gaussian parameter α2, which reduces for a high-f (f = 0.225) sample compared with the pristine host polymer, indicating reduced dynamical heterogeneity, while it is mostly unchanged for the low-f sample. The results highlight that, unlike enthalpic PNCs, entropic PNCs with DPGNPs can modify the host polymer dynamics due to the subtle balance of interactions that occur at different length scales in the matrix.
RESUMO
Viscosity and fragility are key parameters determining the processability and thermo-mechanical stability of glassy polymers and polymer nanocomposites (PNCs). In confined polymers, these parameters are largely dominated by the long relaxation times of the polymers adsorbed at the substrate-polymer interface. On the other hand, for polymer nanocomposites, the interface layer (IL) between the nanoparticles and the surrounding matrix chains often control not only the morphology and dispersion but also various parameters like viscosity and glass transition temperature. Confined PNCs, hence, present a unique opportunity to study the interplay of these two independent interfacial effects. Here, we report the results of X-ray scattering based dynamics measurements of PNC thin films, with a two IL width, unraveling the subtle interplay of these two interfaces on the measured viscosity and fragility. Coupled with coarse-grained molecular dynamics (MD) simulations, our experimental results demonstrate that the viscosity of the PNC films increases with both the IL width and the thickness of the polymer layer adsorbed at the substrate interface. However, while both pristine PS and PNCs with a higher IL width become stronger glasses, as estimated by their fragility, the PNC with a lower IL width shows an increase in fragility with increasing confinement. Our results suggest a novel method to control thermo-mechanical properties and stability of PNC coatings by independently controlling the two interfacial effects in athermal glassy PNCs.
