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Studies on the surface modification of commercial styrene-butadiene-styrene (SBS) rubber with different carbon black (CB) nanofiller content (10–80 parts per hundred parts of rubber (phr)) performed by low-pressure oxygen plasma are presented in this paper. The adhesion properties of the rubber were determined by the peel test for adhesive-bonded joints prepared with a water-based polyurethane (PU) adhesive. The chemical structure and morphology of the SBS rubber surface before and after plasma treatment were investigated by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), respectively. The peel tests showed that the plasma treatment significantly improved the strength of adhesive-bonded joints in the entire range of CB tested, revealing a clear maximum for approximately 50 phr of CB. It was also found that as a result of plasma treatment, functional groups that are responsible for the reactions with the PU adhesive, such as C−OH and C=O, were formed, and their concentration, similar to the peel strength, showed maximum values for approximately 50 phr CB. The occurrence of these maxima was explained using the bound rubber model.

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 (O2, CO2, and CCl4) 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 O2 plasma (electron process) and other plasmas tested (ionic processes).

An attempt to replace a wet chemical surface modification of styrene-butadiene elastomers (SBS), improving their adhesion to polyurethane dispersion adhesives, with a clean low-pressure plasma technique was undertaken. Investigations were performed on commercial SBS rubbers. The plasma was generated by an RF discharge (13.56 MHz, plate electrode reactor) in pure argon (Ar). The rubbers surfaces were investigated by 180°-peel tests and scanning electron microscopy (SEM). The presented results indicate that the plasma treatment is a very promising method of improving the adhesion properties of commercial SBS rubbers elastomers and it should replace the wet chemical methods in industry.

DOI: http://dx.doi.org/10.5755/j01.ms.18.2.1914