Low-Temperature Plasma Modification of Styrene–Butadiene Block Copolymer Surfaces for Improved Adhesion—A Kinetic Approach

This paper proposed a kinetic model that can describe the changes in the adhesion properties of styrene–butadiene (SBS) block copolymer surfaces under the influence of low-temperature plasma treatment. As a measure of these changes, the peel strength of joints formed between the copolymer surface and the polyurethane adhesive was chosen. Five types of low-temperature low-pressure RF plasma, two inert plasmas (Ar and He), and three reactive plasmas (O(2), CO(2), and CCl(4)) were tested. It was found that for all these types of plasma, the peel strength with the plasma treatment time first increases rapidly reaching a maximum value, and then there is a visible decrease in peel strength, after which the peel strength increases again. This dependence of the peel strength on the plasma treatment time is very well described by the proposed model, which considers three processes: (1) the generation of radical states followed by the creation of functional groups involved in the adhesive bonding process, (2) the surface cross-linking that decreases the concentration of these functional groups, and (3) the formation of nano-roughness. The model analysis revealed differences between the action of reactive and inert plasmas in the SBS surface cross-linking mechanism and preferential etching process, as well as differences in the generation of radical states between the O(2) plasma (electron process) and other plasmas tested (ionic processes).