Solution properties of poly(amic acid)–NMP containing LiCl and their effects on membrane morphologies

Physical properties of poly(amic acid) (PAA) casting solutions in N-methyl-2-pyrrolidone (NMP) containing lithium chloride (LiCl) were characterized by viscometry and dynamic light scattering (DLS) and were related to the morphological properties of asymmetric membranes prepared from these solutions. At a fixed polymer concentration, the increase in viscosity of the PAA solutions with increasing LiCl content is mainly determined by the viscosity of the salt–solvent medium, implying that the LiCl–NMP interactions are stronger than those between LiCl and PAA. Because of the strong salt–solvent interactions, complexes between LiCl and NMP are formed. The complexes reduce the solvent power of NMP for PAA inducing polymer aggregation (clustering) and/or transient cross-links in the solutions. Dynamic light scattering results for salt-containing solutions at low PAA concentrations support the existence of these aggregations. Solutions without salt showed a single relaxation, but solutions with LiCl exhibit multiple relaxation modes; two diffusional modes of cooperative and aggregates, and one angle independent transient network mode. The polymer aggregates and transient cross-links form a gel-like structure in the casting solution film and hinder macrovoid formation during phase inversion, resulting in asymmetric membranes with a primarily sponge-like structure.