A method was developed for the entrapment of water-insoluble hydrophobic polymers in a metallic matrix, thus generalizing further the routes for obtaining the novel organics@metal composite materials. The reaction took place in an organic phase using the reduction of metal ions by DMF in the presence of water. The reductive entrapment of polyaniline was studied in detail using XRD, SEM, BET, TGA, UV-vis, XPS, and density measurements, and the mechanism of the entrapment was established. The scope of this approach is demonstrated by entrapment of two additional hydrophobic polymers, polystyrene and polyacrylonitrile.

By employing the new methodology of entrapment of organic molecules within metals, we demonstrate the ability to modify the conductivity of a metal by suitable polymer entrapment. Specifically, polyaniline (PANI) in two molecular weights was entrapped in silver at different concentrations and a comprehensive comparison was preformed for a range of the composite properties, characterized by XRD, SEM, BET, TGA, and density measurements. Pressed films were utilized to measure the electrical conductivity of the composites in order to study the PANI‐silver interactions at the molecular level and to establish a correlation between the microscopic morphology and the film conduction. Such correlations have been identified, and are interpreted. This work extends the functional applications of the new metallic composites and offers insight on the polymer‐metal molecular level interactions.

A new method for the preparation of metal-polymer composite materials is described. This new approach of doping of metals is based on the thermolysis of a zero-valent complex. Specifically, several polymer@Fe-composite powders were[a]

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