Infrared spectroscopy of interphases between model rubber compounds and plasma polymerized acetylene films

Thin (similar to 750 Angstrom) 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, diaryi-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 of cobalt 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.