Thin (750 A) plasma-polymerized films of acetylene were deposited onto polished steel substrates in an inductively coupled r.f. reactor. The films were characterized by x-ray photoelectron spectroscopy (XPS), Fourier-transform infrared spectroscopy (FTIR), Auger electron spectroscopy (AES) and secondary ion mass spectrometry (SIMS) immediately after deposition and after aging in the atmosphere. The FTIR spectra of the as-deposited films were characterized by bands related to mono-and disubstituted acetylene groups and by bands related to methyl and methylene groups. During exposure to the atmosphere, bands related to acetylenic groups decreased in intensity while new bands due to carbonyl group appeared. When XPS spectra were obtained from films that were exposed to the atmosphere, new components assigned to oxidation products were observed in the C 1s spectra that were not observed for as-deposited films, verifying that oxidation had occurred. Numerous peaks related to aromatic structures were observed in positive SIMS spectra of as-deposited films. Results obtained from AES showed that the plasma-polymerized films were continuous and that the oxide on the substrate surface was partially reduced during deposition.Plasma-polymerized acetylene films were excellent primers for rubber-to-steel bonding. Miniature lap joints were prepared by using rubber as an 'adhesive' to bond together pairs of polished steel adherends primed with plasma-polymerized acetylene films. The force required to break the as-prepared joints was -2000 N for a bonded area of 64 mmz and failure was 100% cohesive in the rubber. Similar results were obtained for joints prepared using polished brass substrates.Because of the complexity of reactions between rubber and the plasma-polymerized primer, a model 'rubber' consisting of a mixture of squalene, zinc oxide, carbon black, sulfur, stearic acid, cobalt naphthenate, N,Ndicyclohexylbenzothiazole sulfenamide and diaryl-p-diphenyleneamine was used to simulate the cross-linking reaction. The results obtained using XPS, SIMS, AES and FTIR showed that sulfur diffused through the primer to form a layer of sulfide at the primerlsubstrate interface. Zinc and cobalt sulfides and perthiomercaptides, which formed at the interface between squalene and the plasma-polymerized acetylene primer, catalyzed the reaction between squalene and the primer. Cross-links between squalene and the primer were mostly mono-sullidic, although some evidence for di-and trisullidic cross-links was observed.

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 (ϳ 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 OOH and CAO groups was also obtained. The molecular structure of thin films (ϳ 60 Å) was similar although evidence was obtained to indicate that acetylide groups (HOC'C Ϫ ) 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 { } COOO and { } CAO 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.

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Thin ( -750 A) plasma polymerized films of acetylene deposited onto polished steel substrates are promising primers for rubber-to-metal bonding. The as-deposited films contained mono-and di-substituted acetylene groups, aromatic groups, and groups such as carbonyl which apparently resulted from reaction of residual free radicals with oxygen when the films were exposed to the atmosphere. There was some evidence for formation of acetylides in the interphase between the films and the substrates. Reactions occurring in the interphase between the plasma polymerized films and natural rubber were simulated using a model "rubber" consisting of a mixture of squalene, zinc oxide, carbon black, sulfur, stearic acid, diaryl-p-diphenyleneamine, and N, N-dicyclohexyl-benzothiazole sulfenamide (DCBS). It was found that zinc oxide reacted with stearic acid to form zinc stearate in the interphase between squalene and the plasma polymerized acetylene primer. Zinc stearate reacted with DCBS and sulfur to form an accelerator complex and zinc perthiomercaptides. The perthiomercaptides reacted with squalene and the plasma polymer to form pendant groups which eventually reacted to form crosslinks between squalene and the primer. In the absence ofcobalt naphthenate, the formation of pendant groups and eventually crosslinks was relatively slow and the length of the sulfur chains in the crosslinks and the pendant groups was relatively long. When cobalt naphthenate was added to the model "rubber," the reactions in the interphase between squalene and the plasma polymerized film occurred much faster and the length of the crosslinks and the pendant groups was much shorter.

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