Diffusion of metals in polymers

First information on metal diffusion in polymers resulted from surface spectroscopies which mainly provided insight into chemical interactions of metals at polymer surfaces and into their growth mode. Medium energy ion scattering, electron microscopy, atomic force microscopy, and second-harmonic generation revealed a strong tendency of metals of low and intermediate reactivity to form clusters when deposited onto polymers. The interplay of diffusion and aggregation was also studied by Monte Carlo simulations. Metal diffusivities were obtained from radiotracer and Rutherford backscattering measurements. The available results show that reactive metals do not have any long-range mobility and are effective diffusion barriers. In contrast, isolated atoms of less reactive metals diffuse deep into polymers at elevated temperatures. However, the very pronounced aggregation tendency of these metals effectively impedes diffusion unless they are deposited at rates of the order of monolayers per minute or lower. Nevertheless, traces of noble metals always diffuse into polymers during the early stages of metal deposition, whereas no significant diffusion occurs from a continuous metal film. Even noble metal diffusivities are many orders of magnitude smaller than diffusivities of non-reactive gas molecules and largely decoupled from polymer dynamics. This is attributed to a pronounced reduction in the local chain mobility near metal atoms, e.g., by temporary metal-atom-induced crosslinking.