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Projecting dynamic heterogeneity into nanoconfinement: the enduring legacy of the Long-Lequeux model
1Polymer and Soft Matter Dynamics, Experimental Soft Matter and Thermal Physics (EST), Université libre de Bruxelles (ULB), 1050, Brussels, Belgium. simone.napolitano@ulb.be.
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In the early 2000s, Long and Lequeux established the first quantitative link between dynamic heterogeneity in the bulk and shifts in the glass transition temperature of thin films. Their minimal mean-field model demonstrated that equilibrium density fluctuations give rise to nanometric slow domains, the percolation of which governs vitrification. By showing how geometrical confinement alters this percolation pathway, they predicted shifts using only bulk properties, without fitting interfacial parameters. This conceptual breakthrough, in which finite-size effects emerge from projecting bulk dynamic heterogeneity onto a restricted geometry, constitutes the enduring legacy of their work. Subsequent experiments have confirmed this picture, showing that depression in free-standing films scales with the thickness of a liquid-like surface layer, while in supported systems mobility gradients reflect the reorganization of slow domains anchored at the interface. Looking forward, I outline at the end of this perspective several possible directions for refining this framework so as to capture a broader spectrum of relaxation channels, thereby enriching our understanding of dynamics in both bulk and confined polymer melts.
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