Facile fabrication of mesostructured natural rubber/silica nanocomposites with enhanced thermal stability and hydrophobicity

Natural rubber (NR)/hexagonal mesoporous silica (HMS) nanocomposites (NRHMS) with enhanced thermal and hydrophobic properties were facilely prepared via in situ sol–gel formation with pH adjustment using a low sulphuric acid (H(2)SO(4)) acid concentration. The effect of the amount of 0.5 M H(2)SO(4) (2.5–10 g) added into the pre-synthesis mixture on the physicochemical properties of the obtained NRHMS nanocomposites was investigated. With a small addition of H(2)SO(4) solution, the fabricated NRHMS nanocomposite possessed an improved wormhole-like mesostructure arrangement with a thicker silica wall, which retarded the thermal decomposition of the NR phase, as deduced from the auto-oxidation of NR by thermogravimetric analysis. The H(2)O adsorption–desorption measurement revealed an increased hydrophobicity of the NRHMS composites, explained by the acid-catalyzed bridging of free silanol groups to siloxane bonds, which was supported by the X-ray photoelectron spectroscopy analysis. Scanning transmission electron microscopy with energy dispersive X-ray spectroscopy elemental mapping revealed a good dispersion of the NR phase within the mesostructured silica. However, a high amount of added H(2)SO(4) solution led to silica–NR phase separation due to the decreased hydrophobic interaction between the silica precursor and rubber chain, as well as an agglomeration of the NR phase itself. The mechanism of NRHMS nanocomposite formation under pH-controlled conditions was proposed to proceed via a cooperative self-assembly route.