Published online by Cambridge University Press: 21 February 2011
We have studied the reactions occurring for the deposition of chromium onto pyromellitic dianhydride -4,4′-oxydianiline (PMDA-ODA) polyimide for a wide range of metal coverages, using X-ray photoelectron spectroscopy as well as solution studies involving model compounds. A multi-step, coverage-dependent, mechanism is proposed which includes an initial electron transfer from Cr to PMDA-ODA. followed by formation of Cr-O and and Cr-N polymer-bound intermediates, At higher metal coverage, Cr-oxides and Cr-nitrides are formed which may activate the polymer for subsequent formation of Cr-carbide. No evidence was obtained in support of a model involving initial formation of a π-arene complex between chromium atoms and PMDA-ODA. In the course of this work we have shown that similarities exist between the chemistry of metal atoms in condensed phases and the reactions occurring between metal atoms and surfaces.