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Oxidation of polyethylene (PE) melts in contact with metals (Cu, Pb, Au, Al, Zn, Ag) has been studied by infrared spectroscopy and differential thermal analysis (DTA). These metals may be divided into two groups, depending on their activity for oxidizing PE: namely, high‐activity metals (Cu, Pb, Ag, Zn) and low‐activity metals (Al, Au). During the oxidation of PE in contact with high‐activity metals dissolution of the surface layer of metal is observed with accumulation of metal‐containing compounds (salts of carboxylic acids) in the bulk of the polymer. With low‐activity metals these phenomena are not observed. The rate of oxidation of PE on low‐activity metals approaches the oxidation rate of nonmetals (polytetrafluoroethylene and inorganic glass). With certain high‐activity metals (Cu, Pb) the process of oxidation is accelerated only in the early stage of oxidation; then the oxidation rate slows down and the oxidation process ceases. PE films separated from metal after being oxidized on it possess chemical memory, i.e., their oxidation rate depends on the nature of the metal with which they had been in contact, and on the duration of the contact oxidation. The effect of salts of carboxylic acids (metal stearates) on the oxidation of PE melts was also studied. Based on the data obtained, it is concluded that the rate of oxidation of PE melts on high‐activity metals is controlled by metal‐containing compounds which are the products of contact reactions.

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