Exploring pathways to equilibrate Langmuir polymer films

Focusing on the phase-coexistence region in Langmuir films of poly L-lactide, we investigated changes in non-equilibrated morphologies and the corresponding features of the isotherms induced by different experimental pathways of lateral compression and expansion. In this coexistence region, the surface pressure Π was larger than the expected equilibrium value and was found to increase upon compression, i.e., exhibited a non-horizontal plateau. As shown earlier by using microscopic techniques (Langmuir 2019, 35, 6129–6136), in this plateau region, well-ordered mesoscopic clusters coexisted with a surrounding matrix phase. We succeeded in reducing Π either by slowing down the rate of compression or through increasing the waiting time after stopping the movement of the barriers, which allowed for relaxations in the coexistence region. Intriguingly, the most significant pressure reduction was observed when recompressing a film that had already been compressed and expanded, if the re-compression was started from an area value smaller than the one anticipated for the onset of the coexistence region. This observation suggests a “selfseeding” behavior, i.e., pre-existing nuclei allowed to circumvent the nucleation step. The decrease in Π was accompanied by a transformation of the initially formed metastable mesoscopic clusters into a thermodynamically favored filamentary morphology. Our results demonstrate that it is practically impossible to obtain fully equilibrated coexisting phases in a Langmuir polymer film, neither under conditions of extremely slow continuous compression nor for long waiting times at a constant area in the coexistence region which allow for re-organization.