Molecular structure of interfaces between plasma‐polymerized acetylene films and steel substrates

Abstract Plasma‐polymerized films of acetylene were deposited onto steel substrates in an inductively coupled reactor by exciting the plasma in an argon carrier gas and then injecting the monomer into the afterglow region. The molecular structure of the film/substrate interface was determined using reflection–absorption infrared spectroscopy (RAIR) and X‐ray photoelectron spectroscopy (XPS) to characterize the films as a function of thickness. RAIR showed that thick (∼ 900 Å) as‐deposited plasma‐polymerized acetylene films had a complicated molecular structure and contained methyl and methylene, mono‐ and disubstituted acetylene, vinyl, and cis ‐ and trans ‐disubstituted olefin groups. Evidence of oxidation resulting from the reaction of trapped radicals with atmospheric oxygen and moisture to form O—H and C=O groups was also obtained. The molecular structure of thin films (∼ 60 Å) was similar although evidence was obtained to indicate that acetylide groups (H—C≡C − ) were present at the film/substrate interface. Results obtained using angle‐resolved XPS analysis showed that carbonaceous contamination was removed from the substrate and that oxides and hydroxides on the substrate surface, especially FeOOH, were chemically reduced during deposition of the films. XPS also confirmed that plasma‐polymerized acetylene films deposited on steel substrates contained ${\backslash\atop/}\hbox{C--O-- and}{\backslash\atop/}\hbox{C}=\!\!=\hbox{O}$ groups. Preliminary results also showed that films deposited in an inductively coupled reactor were good primers for rubber‐to‐metal bonding, whereas films deposited in a capacitively coupled reactor were not. The differences may be due to the wide variety of functional groups found in the former type of films but not in the latter. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 1283–1298, 1998