Taking a Tailored Approach to Material Design: A Mechanistic Study of the Selective Localization of Phase-Separated Graphene Microdomains

To achieve multifunctional properties using nanocomposites, selectively locating nanofillers in specific areas by tailoring a mixture of two immiscible polymers has been widely investigated. Forming a phase-separated structure from entirely miscible molecules is rarely reported, and the related mechanisms to govern the formation of assemblies from molecules have not been fully resolved. In this work, a novel method and the underlying mechanism to fabricate self-assembling, bicontinuous, biphasic structures with localized domains made up of amine-functionalized graphene nanoplatelets are presented, involving the tailoring of compositions in a liquid processable multicomponent epoxy blend. Kinetics studies were carried out to investigate the differences in reactivity of various epoxy-hardener pairs. Molecular dynamics simulations and in situ optical photothermal infrared spectroscopy measurements revealed the trajectories of different components during the early stages of polymerization, supporting the migration (phase behavior) of each component during the curing process. Confirmed by the phase structure and the correlated chemical maps down to the submicrometer level, it is believed that the bicontinuous phase separation is driven by the change of the miscibility between various building blocks forming during polymerization, leading to the formation of nanofiller domains. The proposed morphology evolution mechanism is based on combining solubility parameter calculations with kinetics studies, and preliminary experiments are performed to validate the applicability of the mechanism of selectively locating nanofillers in the phase-separated structure. This provides a simple yet sophisticated engineering model and a roadmap to a mechanism for fabricating phase-separated structures with nanofiller domains in nanocomposite films.