A qualitative skin layer formation mechanism for membranes made by dry/wet phase inversion

Optimized membranes made by a dry/wet phase inversion process using forced‐convective evaporation consist of an ultrathin and pore‐free skin layer supported by a nodular transition layer underlying open‐cell, sponge‐like substructure. It is suggested that the out‐ermost region of such case membranes undergo phase separation by spinodal decomposition in the initial stages of the evaporation process. As a result of the small scale of phase separation present in polymer‒solvent systems, an appreciable capillary pressure occurs in the interstitial space filled with the polymer‐poor phase in contact with air. The resulting force acts normal to the membrane–air interface, which tends to consolidate the polymer‐rich phase to form a nonporous surface layer. © 1993 John Wiley & Sons, Inc.