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Effect of microstructure on polymer chain dynamics in polyethylene glycol solutions

Effect of microstructures and interactions on segmental dynamics in polyethylene glycol (PEG) solution in water is probed with macro-scale oscillatory rheology and micro-scale diffusion of a fluorescent probe. PEG solution fluorescence recovery after photobleaching (FRAP) curves have immobile fractions which increase with PEG concentration, for PEG volume fraction (c) > 0.2, indicating structuring. PEG solution micro-scale diffusion coefficients follow Rouse scaling D {\ alpha} c^(-0.54) for c < 0.8, resembling unentangled neutral polymers in good solvent. Addition of nanoclay bentonite (B) in PEG matrix slows down probe diffusion 3-7 times, with heterogeneous dynamics. With addition of carboxymethyl cellulose (CMC) in PEG matrix, probe diffusion is homogeneous with negligibly small enhancement in diffusion time. The macroscale storage modulii for PEG, PEG+B, and PEG + CMC solutions scale as viscous fluid-like, followed by short elastic plateau. Beyond the elastic plateau, the scaling is a concentration-dependent power law greater than the Rouse scaling of 0.5 for 0.1<c<0.2 PEG solutions. We identify a time scale τ_b due to intermolecular interactions in PEG, such that for ω>τ_b^(-1) , Rouse scaling is recovered. Addition of CMC to PEG also restores Rouse scaling. Addition of B gives contributions from both polymer matrix and network of B particles, leading to departure from pure Rouse behaviour. Static microstructural studies reveal clay aggregation due to depletion interactions on increasing the concentration of clay particles in PEG matrix, which leads to a non-monotonic concentration dependence of storage modulus with c.