This invention is directed to a process for the rapid in-situ curing of polymerizable materials to provide macromolecular networks and articles of manufacture that are “morphology-trapped”; that is, they exhibit a fixed phase morphology and/or molecular orientation that is locked in by the curing step. The process includes the steps of mixing together a dead polymer, a reactive plasticizer and an initiator to give a polymerizable composition; further processing the mixture in order to achieve a desired phase morphology and/or molecular orientation of the polymeric constituents; shaping the polymerizable composition into a desired geometry; and exposing the polymerizable composition to a source of polymerizing energy, without mixing, to give a final product with the desired phase morphology and/or molecular orientation locked in place. The phase morphology and molecular orientation present just prior to cure of the polymerizable composition is subsequently trapped or locked in place by the curing step so that further changes in morphology are hindered or prevented.