Study of the multilayered nanostructure and thermal stability of PMMA/PS amorphous films

The nanolayered structure of a forced-assembly of two immiscible amorphous polymers, prepared by layer-multiplying coextrusion, is analyzed for the first time by means of USAXS. The experimental long spacings for the series of PMMA/PS films studied show a good correlation with the nominal periodicity values of the stacks. In addition, the long spacings, derived from a localized area in AFM, are also in good agreement with the USAXS values averaged over much larger areas. The structural variation, after thermal treatment, of two samples with nominal periodicities of 174 and 215 nm is reported. In the range RT-140 °C, the nanolayered structure is mostly well preserved as evidenced by AFM. However, the absence of USAXS maxima after annealing at temperatures included in the above range has been tentatively explained by interfacial coarsening and spinodal dewetting occurring between the forced-assembled polymer layers. Above 140 °C, the interfacially driven break-up of the layers ends up with the final disappearance of the multilayered structure.