Molecular Structure of the Interphase Formed by Plasma-Polymerized Acetylene Films and Steel Substrates

Abstract

The molecular structure of the interphase between plasma-polymerized acetylene films and steel substrates was determined using in situ reflection–absorption infrared spectroscopy (RAIR) and X-ray photoelectron spectroscopy (XPS). Plasma-polymerized acetylene films were deposited onto polished steel substrates using argon as a carrier gas and inductively coupled, radio frequency (RF)-powered plasma reactors that were interfaced directly to the XPS and Fourier transform infrared (FTIR) spectrometers. RAIR showed that the plasma polymerized films contained large numbers of methyl and methylene groups but only a small number of mono substituted acetylene groups, indicating that there was substantial rearrangement of the monomer molecules during plasma polymerization. Bands were observed near 1020 and 855 cm−1 in the RAIR spectra that were attributed to skeletal stretching vibrations in C–C–O–Fe groups, indicating that the plasma-polymerized films interacted with the substrate through formation of alkoxide bonds. Another band was observed near 1565 cm−1 and attributed to carboxylate groups in the interphase between the films and the oxidized surface of the substrate. Results obtained from XPS showed that the surface of the iron substrate consisted mostly of a mixture of Fe2O3 and FeOOH and that iron was mostly present in the Fe(III) oxidation state. However, during plasma polymerization of acetylene, there was a tendency for the concentration of FeOOH groups to decrease and for the concentration of Fe(II) to increase, due to the reducing nature of argon/acetylene plasmas. Results from XPS also confirmed the formation of alkoxide and carboxylate groups in the interphase during plasma polymerization of acetylene.