par Di Leva, Chiara 
;Song, Zijian ;Caporaletti, Federico ;Schweicher, Guillaume ;Napolitano, Simone
Référence Macromolecules, 59, 14, page (8476–8485)
Publication Publié, 2026-07-06
;Song, Zijian ;Caporaletti, Federico ;Schweicher, Guillaume ;Napolitano, Simone Référence Macromolecules, 59, 14, page (8476–8485)
Publication Publié, 2026-07-06
Article révisé par les pairs
| Résumé : | Adsorption of polymer melts on solid substrates exhibits slow, nonexponential kinetics, including extended logarithmic regimes commonly attributed to loop-controlled adsorption and progressive surface crowding. Logarithmic growth is a hallmark of polymer melt adsorption, not shared by small molecules or polymers in dilute solution. Here, we show that this behavior emerges naturally within a unified spectral framework, in which the kinetics are formulated as a superposition of thermally activated processes sharing a common activation barrier but spanning a broad spectrum of prefactors. The two kinetic regimes map onto distinct spectral windows: train-dominated adsorption at short times corresponds to a flat rate distribution, while the subsequent loop-controlled slowdown is associated with a log-uniform spectrum, sharing common patterns with logarithmic relaxations observed in the aging of electron glasses and relaxation of crumpled sheets. Saturation is determined by the lower bound of the spectrum, and we establish explicit relations connecting both spectral cutoffs directly to experimentally accessible observables. The framework accounts for time–temperature superposition, the invariance of the crossover and saturation values with temperature, and the experimentally observed constancy of the ratio between linear and logarithmic growth rates. Finally, we show that it is possible to extract the bounds of the rate spectrum directly from standard kinetic parameters without requiring explicit fitting of the full model equations. |
