Time Allowed for Equilibration Quantifies the Preparation Induced Nonequilibrium Behavior of Polymer Films

Performance and properties of materials may strongly depend on processing conditions. This is particularly so for polymers, which often have relaxation times much longer than the processing times and therefore may adopt preparation dependent non-equilibrated molecular conformations that potentially cause novel properties. However, so far it was not possible to predictably and quantitatively relate processing steps and resulting properties of polymer films. Here, we demonstrate that the behavior of polymer films, probed through dewetting, can be tuned by controlling preparation pathways, defined through a dimensionless parameter p, which is the appropriate preparation time normalized with the characteristic relaxation time of the polymer. We revealed scaling relations between p and the amount of preparation-induced residual stresses, the corresponding relaxation time, and the probability of film rupture. Intriguingly, films of the same thickness exhibited hole nucleation densities and subsequent dewetting kinetics differing by up to an order of magnitude, indicating possibilities to adjust the desired properties of polymer films by preparing them in appropriate ways.