Polymer tethered graphene oxide influences miscibility and cooperative relaxation in LCST blends

The miscibility of a classical lower critical solution temperature (LCST) system; PMMA/SAN was probed by different rheological fingerprints such as isochronal temperature ramps, and isothermal frequency sweeps, in presence of graphene oxide (GO) and PMMA tethered GO. The chain length of the grafted polymer was varied to study its effect on miscibility, volume cooperativity, entanglement density and localization in the blends. The PMMA tethered GO alters the chain dynamics both at local and cooperative length scale through entropic and enthalpic interactions. It was perceived that the thermodynamic miscibility, cooperative relaxations and concentration fluctuation in PMMA/SAN blends are controlled by the spatial distribution of GO in the blend. By varying the chain length, we were able to understand that shorter tethered chains lead to early phase separation whereas the tethered chain length similar to that of the host matrix delays phase separation. Interestingly, irrespective of the length of the tethered polymer chain, the grafted GO sheets were not localized in the thermodynamically preferred phase (here PMMA). These findings are of great importance to further help us understand the theories and simulations which pertain to chain dynamics of PMMA/SAN blends containing polymer-tethered nanoparticles with large specific surface area like GO.