We investigate the physical foaming process of glassy poly(ether imide) and poly(ether
sulfone) using carbon dioxide and report temperature−concentration diagrams (“foam diagrams”) marking
out the foaming envelope in which dense CO2-saturated films expand and microvoids are introduced.
Two types of porosities are observed. Closed microcellular structures occur at carbon dioxide saturation
levels below 50 cm3 (STP)/cm3 (polymer); nanoporous bicontinuous (open) structures with pore sizes as
small as 40 nm occur above this CO2 concentration threshold, which is identical for both polymers. The
cellular-to-bicontinuous transition is characterized in detail on the basis of gas permeation measurements
and is represented as a separate window inside the foaming diagram. In this paper, the transition to
bicontinuous structures is reported for the first time, and its generic physical basis is critically reviewed.
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