Layer-by-layer assembly of salt-containing polyelectrolyte complexes for the fabrication of dewetting-induced porous coatings

The layer-by-layer (LbL) assembly of salt-containing nonstoichiometric polyelectrolyte complexes (PECs) with oppositely charged uncomplexed polyelectrolyte for the fabrication of dewetting-induced porous polymeric films has been systematically investigated. Salt-containing poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA) complexes (noted as PAH-PAA) with a molar excess of PAH were LbL assembled with polyanion poly(sodium 4-styrenesulfonate) (PSS) to produce PSS/PAH-PAA films. The structure of the PAH-PAA complexes is dependent on the concentration of NaCl added to their aqueous dispersions, which can be used to tailor the structure of the LbL-assembled PSS/PAH-PAA films. Porous PSS/PAH-PAA films are fabricated when salt-containing PAH-PAA complexes with a large amount of added NaCl are used for LbL assembly with PSS. In-situ and ex-situ atomic force microscopy measurements disclose that the dewetting process composed of pore nucleation and pore growth steps leads to the formation of pores in the LbL-assembled PSS/PAH-PAA films. The present study provides a facile way to fabricate porous polymeric films by dewetting LbL-assembled polymeric films comprising salt-containing PECs.