Impacts of Polymer Adsorption on Adhesion Strength at Solid Interfaces

Polymer adhesion on solids is governed by chain aggregation at interfaces, yet isolating intrinsic adhesion strength (G₀) from complex failure modes has remained elusive. Here, a surface and interfacial cutting analysis system (SAICAS) was used to quantify G₀ from thickness-dependent measurements. Polystyrene films with varied molecular weights and poly(methyl methacrylate) with different stereoregularities were analyzed as a function of thermal annealing time. G₀ increased with the growth of the adsorbed layer. At extended annealing times, absolute G₀ was dictated not by molecular weight but by segment-substrate interaction energy and chain conformation influenced by stereoregularity. These findings establish that interfacial adhesion is determined primarily by the total interaction energy from chain contact points with the solid. This study provides molecular-level insights into polymer adhesion and principles for the rational design of high-performance adhesives across applications.