Mesoscale modelling of polymer-mediated adhesion: application to tack tests†

We develop a generic computational methodology to understand and predict adhesion between polymers and solid substrates. The motion of coarse-grained polymer segments is tracked via a hybrid particle-field mesoscopic simulation method (BD/kMC) combining Brownian dynamics (BD) and kinetic Monte Carlo (kMC) for the entanglement dynamics as described by the slip-spring model. The method addresses entangled polymer films capped between solid surfaces under both quiescent and nonequilibrium conditions. The latter entail imposing constant rate extension along the aperiodic (normal) direction, while keeping the lateral dimensions constant. Experimentally relevant length scales and elongation rates can be addressed thanks to the coarse-graining inherent in the approach. These simulations are representative of “tack” tests, employed routinely for assessing the performance of soft adhesive materials. The performance of each interface is characterized by the stress–strain curves, yield stress, and toughness. The failure mechanism is determined upon analyzing the evolution of the stress–strain curve and the morphology of the fractured interfaces. The simulations are conducted over a broad parameter space by varying the rate of elongation, the rate constants for attachment/detachment of polymer segments to/from the surface, and the activation length. The latter describes the coupling with the pulling forces exerted on the particles at the interface by the rest of the polymer. Setting the activation length to zero is suitable for describing strong adhesives or highly compressible materials (foams). Under these conditions, toughness is maximized and increases significantly with elongation rate, sometimes leading to chain fracture. With increasing activation length the toughness of the interface decreases and detachment becomes more efficient at higher elongation rates since the increased stress accelerates the detachment process. In all cases considered here, toughness increases monotonically with adhesion. Furthermore, the yield stress increases consistently with increasing elongation rate due to the inability of the polymer to relax the imposed stress.