Molecular Composite Coatings on Nafion Using Layer-by-Layer Self-Assembly.

Controlled growth of nanometer-scale multilayered coatings of negatively-charged sulfonated poly(benzobisimidazole) (SPBI), complexed with positively-charged poly(2-vinyl pyridine) (P2VP) on quartz and Nafion membrane as substrates has been explored. Both polymers, SPBI and P2VP, possess a net charge in methanol as a result of the dissolution of SPBI by complexation with triethylamine (TEA) and the protonation of P2VP with HCl, respectively, and thereby can form a multilayered molecular composite of alternating anionic SPBI and cationic P2VP via an electrostatic Layer-by-Layer (LbL) self-assembly. UV-Vis absorption spectrophotometry was used to monitor the build-up and growth rate of such SPBI/P2VP multilayer films. Atomic Force Microscopy (AFM) was used to determine the roughness and thickness of the resulting SPBI/P2VP multilayers. As a result, it was found that a steady-state linear growth regime for the LbL self-assembled SPBI/P2VP multilayer films and coatings onto quartz and Nafion membranes was observed after completion of the first few deposition cycles, indicating the successful formation of the SPBI/P2VP multilayered assembly in methanol solutions. In addition, the SPBI/P2VP multilayer films in the perpendicular direction (flat view) demonstrated isotropic orientation distribution on the Nafion™ membrane, while the SPBI/P2VP multilayer films examined by x-ray scattering in the parallel direction (edge view) revealed anisotropic orientation, the combined observations indicated confinement of SPBI rods to the plane of the coating. We further found that the SPBI/P2VP multilayer coated Nafion possesses good thermal stability, as indicated by isothermal gravimetric analysis at 310 °C. It was also observed that SPBI/P2VP multilayer coatings using the LbL self-assembly technique on Nafion membrane significantly increased the membrane stiffness, despite the small coating thickness employed.