Graphene–polyelectrolyte multilayer film formation driven by hydrogen bonding

Abstract

A method for preparing hydrogen bonded multilayer thin films comprised of layer pairs of surfactant stabilized graphene and an anionic polyelectrolyte is described. The films were constructed at low pH using the Layer-By-Layer (LbL) technique, where the adsorption of the cationic polyelectrolyte, polyethyleneimine (PEI) is followed by the sequential alternating adsorption of the anionic polyelectrolyte, polyacrylic acid (PAA) and anionic graphene sheets modified with Pluronic® F108, a polyethylene oxide–polypropylene oxide–polyethylene oxide (PEO–PPO–PEO) surfactant. Quartz Crystal Microbalance (QCM) measurements indicate that film formation was driven by hydrogen bonding between the carboxylic acid group of the PAA and ethylene oxide unit present in the surfactant. QCM measurements and Raman spectra showed evidence of non-linear and linear growth at low and high numbers of adsorbed layers respectively, suggesting overall superlinear film growth. Atomic Force Microscopy (AFM) Quantitative Nanomechanical Mapping (QNM) measurements of the films indicated that the reduced Young’s Modulus of the films decreased with increasing numbers of adsorbed layers, reaching a bulk value of 6.07–32.3MPa for samples with greater than 300 layers of surfactant stabilized graphene and PAA. The films were also shown to deteriorate partially with aqueous solutions at neutral and basic pH. The thin films exhibited features advantageous for use in coatings, such as pH responsiveness in addition to different mechanical properties, surface roughness, and internal structures based on the number of layers adsorbed.