Synergistic effect of plasma-modified halloysite nanotubes and carbon black in natural rubber-butadiene rubber blend

Halloysite nanotubes (HNTs) were investigated concerning their suitability for rubber reinforcement. As they have geometrical similarity with carbon nanotubes, they were expected to impart a significant reinforcement effect on the rubber compounds but the dispersion of the nanofillers is difficult. In this work, HNTs were surface-modified by plasma polymerization to change their surface polarity and chemistry and used in a natural rubber/butadiene rubber blend in the presence of carbon black. The aim of the treatment was to improve the rubber–filler interaction and the dispersion of the fillers. A thiophene modification of HNTs improved stress–strain properties more than a pyrrole treatment. The surface modification resulted in a higher bound rubber content and lower Payne effect indicating better filler–polymer interaction. Scanning electron microscopy measurements showed an increased compatibility of elastomers and fillers. As visualized by transmission electron microscopy, the thiophene-modified HNTs formed a special type of clusters with carbon black particles, which was ultimately reflected in the final mechanical properties of the nanocomposites. The addition of HNTs increased loss angle