Polymer–Polymer Interfacial Perturbation on the Glass Transition of Supported Low Molecular Weight Polystyrene Thin Films

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Clarifying interfacial perturbation on polymer relaxation is important for polymer material development. Herein we investigated polymer–polymer interfacial perturbation on low molecular weight (MW) polystyrene (PS) thin film (15–180 nm) glass transition by depositing various polymers atop PS films. Overall, rubbery topcoats induced T g depression of PS thin film (below 60 nm), while glassy topcoats induced T g elevation of PS thin film (below 30 nm). Importantly, for the rubbery topcoat, T g perturbation strength is largely dependent on the T g difference between interfacial polymers and a larger T g difference would induce stronger perturbation, while for the glassy topcoat this dependence is inconspicuous. Meanwhile, the interfacial perturbation length during PS glass transition by rubbery topcoats is estimated to be around 8 nm, while it is considered to be about 3.5 nm for glassy topcoats. The different interfacial perturbation length induced by disparate topcoats was accounted for by their different perturbation strength on adjacent PS molecules and disparate interfacial roughness. The results can promote the understanding of polymer interfacial perturbation and benefit the design and development of polymer-based materials.