Gas permeation and microstructure of reduced graphene oxide/polyethyleneimine multilayer films created via recast and layer-by-layer deposition processes

Nowadays, graphene/polymer composite films with multilayer structure have attracted significant attention for gas barrier application. In this study, a series of reduced graphene oxide/polyethyleneimine (RGO/PEI) composite films were created via recast and layer-by-layer deposition processes. By using the recast process, the myriad PEI molecules in the precursor solution (the PEI : GO feeding ratio is 0.02 : 0.1, 0.05 : 0.1, 0.1 : 0.1, 0.3 : 0.1 and 0.5 : 0.1) ensure more effective reduction and surface modification of the graphene oxide (GO) sheets, while the undesirable free PEI molecules are eventually removed via a filtration process. Then, the RGO/PEI composite films were synthesized on PET substrate using a layer-by-layer assembly. The resulting films show a homogeneous and compact brick-wall structure with excellent gas barrier properties. Barriers against water vapor, nitrogen/oxygen, and carbon dioxide require different content of PEI in the composite film for optimal performance; the ideal values are 19.7, 23.8, and 24.1 wt%, respectively. These values are much lower compared with previously reported studies. Further, the permeability, free volumes, component ratio, morphology, and density of the RGO/PEI composite films have been carefully investigated and discussed. The results revealed that the mechanism behind the excellent gas barrier property of the RGO/PEI composite films is a synergistic effect created by the combination of the brick-wall structure, the small free volume holes, the suitable PEI content (ranging from 19.7 wt% to 24.1 wt%), the high density, and the hydrophobicity.