Using TESPT to Improve the Performance of Kaolin in NR Compounds

Kaolin is an abundant, low-cost filler for elastomeric compounds. The kaolin used here is primarily kaolinite, chemically clean, and contains a fine particle population. Although agglomeration is evident, it can be mitigated by appropriate physical processing and, when desired, by chemical coupling. This study evaluates kaolin in natural rubber (NR) and examines how adding bis(triethoxysilylpropyl) tetrasulfide (TESPT) during mixing affects filler–matrix compatibility, viscoelastic response, cure stability, and mechanical performance. Kaolin was structurally and morphologically characterized, and the compounds were prepared in a closed mixer coupled to a torque rheometer under controlled dispersion conditions. Part 1 assessed NR with kaolin without a coupling agent, and Part 2 assessed the NR–kaolin with TESPT added during mixing (0.5 and 5 phr). Small-amplitude oscillatory shear (SAOS) was used to probe viscoelastic behavior, while oscillating disk rheometry (ODR) and tensile tests quantified cure and mechanical properties. In Part 1, kaolin increased NR stiffness in SAOS and raised the 100% and 300% moduli by about 40% and 50%, respectively, relative to the unfilled NR compound, while reducing cure reversion from 30% to 10% at 150 °C. In Part 2, TESPT produced a threshold-like response: 0.5 phr caused only minor changes, whereas 5 phr led to pronounced stiffening and cure stabilization. At 5 phr, a low-frequency plateau in G′ below 0.1 Hz with no G′–G″ crossover was observed, accompanied by higher MH and ΔM in ODR and reversion suppressed to 1% after 30 min. These trends indicate the formation of a more connected filler-rubber network, promoted by TESPT-assisted interfacial coupling/adhesion, while also reflecting the ability of TESPT (tetrasulfide) to contribute sulfur and modify the curing chemistry. Mechanically, kaolin produced marked stiffness increases, with the 100% and 300% moduli increasing by an additional 9% and 36%, respectively, at 5 phr TESPT. At the same time, ultimate tensile strength remained lower than that of neat NR, and elongation at break decreased slightly. Overall, adding TESPT during mixing enhances interfacial coupling and network connectivity and, at higher loading, also influences cure chemistry, yielding higher modulus and strongly improved reversion resistance without increasing ultimate tensile strength relative to neat NR.