Surfaces of LDPE can be functionalized with primary amino groups using the afterglows from dielectric barrier discharges in N2, N2 + H2, and N2 + NH3 mixtures at atmospheric pressure. Quantitative analysis by a recently developed ATR FT‐IR spectroscopic method allows calculation of the number of NH2 groups generated per unit area. Treatment in N2 + H2 afterglows was found to be most efficient in terms of area densities of primary amines achieved (more than 15 nm−2), but appreciable quantities of NH2, up to about 3 nm−2, are also obtained in pure N2. Possible mechanisms of the amination reaction and the roles of gas additives are discussed.

The quantitative evaluation of ATR FT‐IR spectra of chemically derivatized plasma‐modified polymer surfaces is proposed in order to derive area densities ρ (numbers or mole numbers per unit area) of chemical functional groups. Because of the very small thickness dmod of the modified surface region, a simple equation can be applied that allows the calculation of ρ from band area measurements on polymer samples and on suitable reference solutions that contain small molecules with the same functional groups. Applying this method to polymer surfaces plasma aminated in atmospheric‐pressure afterglows of N2 + H2 mixtures, an initial amination rate of about 1 nm−2 · s−1 has been determined.

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