An entropy generation approach to the molecular recoiling stress relaxation in thin nonequilibrated polymer films.

In polymers, the equilibrium state is achieved when the chains have access to the maximum number of conformational states, which allows them to explore a larger conformational space, leading to an increase in the entropy of the system. Preparation of thin polymer films using the spin-coating technique results in polymer chains being locked in a nonequilibrium state with lower entropy due to possible stretching of chains during the process. Allowing enough time for recovery results in the relaxation of the spin-coating-induced molecular recoiling stress. Annealing such a film generates entropy due to its inherent irreversibility. We employed the dewetting technique to determine the molecular recoiling stress relaxation time in poly-(tertbutyl styrene) thin films. Furthermore, we qualitatively differentiated the metastable states achieved by the polymer film using entropy generation in a relaxing polymer film as an effect of thermal entropy and associated it with the conformational entropy of polymer chains utilizing the molecular recoiling stress relaxation time. This enabled us to explain molecular recoiling stress relaxation using a rather simplistic approach involving segmental level molecular rearrangements in polymer chains by attaining transient metastable states through an entropically activated process driving toward equilibrium.