title: Organo-Chlorinated Thin Films Deposited by Atmospheric Pressure Plasma-Enhanced Chemical Vapor Deposition for Adhesion Enhancement between Rubber and Zinc-Plated Steel Monofilaments.
abstract: A continuous-flow plasma process working at atmospheric pressure is developed to enhance the adhesion between a rubber compound and a zinc-plated steel monofilament, with the long-term objective to find a potential alternative to the electrolytic brass plating process, which is currently used in tire industry. For this purpose, a highly efficient tubular dielectric barrier discharge reactor is built to allow the continuous treatment of "endless" cylindrical substrates. The best treatment conditions found regarding adhesion are Ar/O2 plasma pretreatment, followed by the deposition from dichloromethane of a 75 nm-thick organo-chlorinated plasma polymerized thin film. Ar/O2 pretreatment allows the removal of organic residues, coming from drawing lubricants, and induces external growth of zinc oxide. The plasma layer has to be preferably deposited at low power to conserve sufficient hydrocarbon moieties. Surface analyses reveal the complex chemical mechanism behind the establishment of strong adhesion levels, more than five times higher after the plasma treatment. During the vulcanization step, superficial ZnO reacts with the chlorinated species of the thin film and is converted into porous and granular bump-shaped ZnwOxHyClz nanostructures. Together, rubber additives diffuse through the plasma layer and lead to the formation of zinc sulfide on the substrate surface. Hence, two distinct interfaces, rubber/thin film and thin film/substrate, are established. On the basis of these observations, hypotheses explaining the high bonding strength results are formulated.
authors.affiliation: †Luxembourg Institute of Science and Technology, 41 rue du Brill, Belvaux, L-4422, Luxembourg.|‡Institut Jean Lamour, UMR 7198 CNRS, Département de Chimie et Physique des Solides et des Surfaces, Université de Lorraine, Parc de Saurupt, CS 50840, Nancy F-54011, France.
authors.forename: Cédric
authors.initials: C
authors.lastname: Vandenabeele
authors.affiliation: †Luxembourg Institute of Science and Technology, 41 rue du Brill, Belvaux, L-4422, Luxembourg.
authors.forename: Simon
authors.initials: S
authors.lastname: Bulou
authors.affiliation: †Luxembourg Institute of Science and Technology, 41 rue du Brill, Belvaux, L-4422, Luxembourg.
authors.forename: Rémy
authors.initials: R
authors.lastname: Maurau
authors.forename: Frederic
authors.initials: F
authors.lastname: Siffer
authors.affiliation: ‡Institut Jean Lamour, UMR 7198 CNRS, Département de Chimie et Physique des Solides et des Surfaces, Université de Lorraine, Parc de Saurupt, CS 50840, Nancy F-54011, France.
authors.forename: Thierry
authors.initials: T
authors.lastname: Belmonte
authors.affiliation: †Luxembourg Institute of Science and Technology, 41 rue du Brill, Belvaux, L-4422, Luxembourg.
authors.forename: Patrick
authors.initials: P
authors.lastname: Choquet
keywords: atmospheric pressure; continuous-flow deposition process; interface characterization; organo-chlorinated thin films; plasma-enhanced chemical vapor deposition; rubber−steel adhesion; surface preparation