Unveiling the Effects of In Situ Layer–Layer Interfacial Reaction in Multilayer Polymer Films via Multilayered Assembly: From Microlayers to Nanolayers.

Multilayered polymer films are increasingly used in the daily life, but their macroscopic properties are always limited by the layer–layer interfacial compatibility. In this work, the influence of interface modification through in situ layer–layer interfacial reaction during a multilayered assembly is revealed from micro‐ to nanolayer films, based on maleated poly(vinylidene fluoride) and polyamide‐6. In the presence of interfacial reaction and confinement, layer architecture and microstructure are highly dependent on the number of layers. Specifically, for nanolayer films having smaller layer thicknesses and higher reaction extent, layer integrity is reduced with the occurrence of interfacial instabilities. Depending on the microstructural evolution from multilayer assembly, those films exhibit quantitatively different extensional rheological and dielectric properties from micro‐ to nanolayers. More importantly, dielectric spectroscopy reveals the contribution of copolymer‐rich interphases to the dielectric performance of micro/nanolayered films. Additionally, charge transport dynamics in nanolayered films also differ significantly from their microlayered counterparts. They are attributed to the strong dependence of interfacial reaction extent and resulting microstructure on the number of layers and layer thicknesses. This work clearly illustrates how the control of layer–layer interfacial reaction in micro/nanolayer assembly can tune the interfacial, microstructure, and macroscopic properties of multilayered products. [ABSTRACT FROM AUTHOR]