Silver–polyimide nanocomposite membranes: Macromolecular‐matrix‐mediated metallization of an aromatic,fluorinated polyimide yielding highly reflective films at low metal concentrations

Highly reflective, surface‐metalized, flexible polyimide films were prepared by the incorporation of a soluble silver‐ion complex, (hexafluoroacetylacetonato)silver(I) (AgHFA), into dimethylacetamide solutions of poly(amic acid) prepared from 2,2‐bis(3,4‐dicarboxyphenyl)hexafluoropropane dianhydride and 2,2‐bis4‐(4‐aminophenoxy)phenyl]hexafluoropropane. The thermal curing of solution‐cast silver(I)–poly(amic acid) films to 300°C led to cycloimidization of the amic acid with concomitant silver(I) reduction and the formation of a reflective, air‐side‐silvered surface at very low (2 wt % and 0.3 vol %) silver concentrations. The reflective surface evolved only when the cure temperature reached about 275°C, although X‐ray diffraction showed metallic silver in the hybrid film by 200°C. After a maximum specular reflectivity greater than 80% was achieved for the 2 wt % silver film, the specular reflectivity diminished sharply with further heating at a constant temperature of 300°C. Incorporating the AgHFA complex into the soluble, fully imidized form of poly{(1,3‐dihydro‐1,3‐dioxo‐2H‐isoindole‐2,5‐diyl)2,2,2‐trifluoro‐1‐(trifluoromethyl)ethylidene](1,3‐dihydro‐1,3‐dioxo‐2H‐isoindole‐5,2‐diyl)‐1,4‐phenyleneoxy‐1,4‐phenylene2,2,2‐trifluoro‐1‐(trifluoromethyl)ethylidene]‐1,4‐phenyleneoxy‐1,4‐phenylene} gave films that were 25% less reflective than those beginning with poly(amic acid). Though highly reflective, the films were not electrically conductive. The metalized membranes were thermally stable and maintained mechanical properties similar to those of the parent polyimide. Transmission electron microscopy revealed an air‐side, near‐surface layer of silver that was about 40 nm thick; the interior of the film had well‐dispersed metal particles with diameters mostly less than 2 nm. The near‐surface silver layer maintained its integrity because of physical entrapment of the metal nanoparticles beneath a thin layer of polyimide; that is, the practical adhesion of the metal layer was good. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2409–2418, 2007