Nano-mechanical imaging reveals heterogeneous cross-link distribution in sulfur-vulcanized butadiene-styrene rubber comprising ZnO particles

The addition of zinc oxide (ZnO) to sulfur (S-) vulcanized rubbers is known to accelerate the cross-linking kinetics and to increase the heterogeneity of the cross-link density. However, the spatial distribution of cross-links is hardly known and the mechanism of the activity of ZnO is disputed. We therefore investigated S-vulcanized butadiene-styrene rubber comprising ZnO particles. The samples were fractured and then investigated employing the nano-mechanical mapping mode (NM) of scanning force microscopy (SFM), supported by scanning electron microscopy (SEM). We find that rubber around the ZnO particles exhibits a higher Young's modulus in a shell with a width up to about 200 nm. Furthermore, the extension and retraction curves on these shells exhibit a smaller hysteresis than on the rubber further away from the ZnO particles. We attribute the higher Young's modulus and the smaller hysteresis to a higher cross-link density in rubber surrounding the ZnO particles and we discuss a mechanism of the activity of ZnO in rubbers which can explain this. (C) 2016 Elsevier Ltd. All rights reserved.