AbstractThis study examines the effect of dynamic vulcanization on the co‐continuous morphology in ethylene‐propylene‐diene terpolymer (EPDM)/polypropylene (PP) blends using a technique of morphology investigation involving focused ion beam (FIB) etching of the sample surface, followed by topological investigation of the sample surface using tapping mode atomic force microscopy (TMAFM). The FIB ion etching rates of EPDM and PP are distinctly different, and these differences create a significant topological contrast between the phases when subsequently analyzed by atomic force microscopy. This approach allows for the high‐resolution observation of dispersed EPDM, and phases as small as 100 nm, are clearly identified. Since it is shown that the etching rates of noncrosslinked and crosslinked EPDM are similar, it was necessary to selectively remove the noncrosslinked EPDM phase by solvent dissolution. This combination of techniques then allows for the clear distinction of polypropylene, as well as noncrosslinked and crosslinked EPDM phases in the blend. The high‐resolution micrographs together with the continuity data, surprisingly, indicate that a noncrosslinked co‐continuous EPDM phase (α‐network) transits to a finer network of crosslinked EPDM (β‐network) after dynamic crosslinking. It is suggested that this β‐network is produced as a result of the viscosity mismatch between the noncrosslinked and crosslinked EPDM melt occurring at the outer envelope of the α‐network during dynamic crosslinking. As the crosslinked material pulls away from the noncrosslinked material under dynamic melt mixing conditions, it creates a smearing effect. It is shown that the initial α‐network maintains its continuity and demonstrates a diminished pore diameter as crosslinking proceeds. Furthermore, when the noncrosslinked material is extracted almost no crosslinked phase (<1%) is found to be present in the extract. These results strongly indicate that the crosslinking proceeds initially at the outer envelope of the EPDM phase, and works its way toward the center. © 2006 American Institute of Chemical Engineers AIChE J, 2006