Abstract
Herein we show that the nanostructured interface obtained via modulation of the pore size has a strong impact on the segmental and chain dynamics of two poly(propylene glycol) (PPG) derivatives with various molecular weights (Mn = 4000 g/mol and Mn = 2000 g/mol). In fact, a significant acceleration of the dynamics was observed for PPG infiltrated into ordinary alumina templates (Dp = 36 nm), while bulklike behavior was found for samples incorporated into membranes of modulated diameter (19 nm < Dp < 28 nm). We demostrated that the modulation-induced roughness reduces surface interactions of polymer chains near the interface with respect to the ones adsorbed to the ordinary nanochannels. Interestingly, this effect is noted despite the enhanced wettability of PPG in the latter system. Consequently, as a result of weaker H-bonding surface interactions, the conformation of segments seems to locally mimic the bulk arrangement, leading to bulklike dynamics, highlighting the crucial impact of the interface on the overall behavior of confined materials.
Highlights
We show that the nanostructured interface obtained via modulation of the pore size has a strong impact on the segmental and chain dynamics of two poly(propylene glycol) (PPG) derivatives with various molecular weights (Mn = 4000 g/mol and Mn = 2000 g/mol)
It should be recalled that the deviation of segmental dynamics and shift of the glass transition of macromolecules deposited as thin films have a finite lifetime and strongly depend on the kinetics of the formation of an irreversibly adsorbed layer that further affects the packing density at the interface.[3,4]
Nano Letters pubs.acs.org/NanoLett variation of this parameter has a strong influence on the mobility of adsorbed molecules and the dynamics of polymer films in general.[13−15] Recently, this supposition was confirmed by experimental data showing that the segmental dynamics of polymers supported as thin layers “prepared under non-equilibrium conditions” was enhanced near the rough interface because of the perturbation of the interfacial free volume and “noncomplete filling of surface asperities”
Summary
Nano Letters pubs.acs.org/NanoLett variation of this parameter has a strong influence on the mobility of adsorbed molecules and the dynamics of polymer films in general.[13−15] Recently, this supposition was confirmed by experimental data showing that the segmental dynamics of polymers supported as thin layers “prepared under non-equilibrium conditions” was enhanced near the rough interface because of the perturbation of the interfacial free volume and “noncomplete filling of surface asperities”.16
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