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The porosity characteristics of a series of 12 macroporous poly(styrene-divinylbenzene) resins have been quantified by the mercury intrusion method and by image analysis of transmission electron micrographs (TEM) of resin particle cross-sections. The results from both methods correlate extremely well. Bearing in mind that the TEM procedure does 'observe' pores more directly than the Hg intrusion method, the present study tends to validate the intrusion procedure and calculations.

SUMMARY We describe the microscopical analysis of two polystyrene divinylbenzene copolymers (PS‐DVB) made using 20 and 55% (v/v) DVB cross‐linker respectively, in which the hydrated structure of each polymeric material solvated in water is preserved by employing very rapid freezing and low‐temperature freeze‐drying techniques. Using the zero‐loss mode of electron spectroscopic imaging to enhance the contrast of unstained polymer sections, we introduce some novel methods for the application of computer‐assisted image analysis for routine examination of polymer pore structure. We also relate these parameters to the ability of the two polymers to absorb nanometre‐sized particles—neutral colloidal gold particles and cationized ferritin. Both methods will be invaluable in the structural analysis of porous polymers, but particularly for comparative analyses of macroporous sorbents.