Payne effect of carbon black filled natural rubber nanocomposites: Influences of extraction, crosslinking, and swelling

Rubber nanocomposites experiencing dynamic shears at large strain amplitudes ( γ ) exhibit the nonlinear Payne effect featured by decays of storage and loss moduli ( G′ and G″ ) or by G′ decay accompanied with G″ overshoot near a critical strain amplitude. The occurrence of the Payne effect has been assigned to damages of “filler network” and rubber-filler interfacial interactions for a long time and to Rouse dynamics of rubber chains recently. To solve the dispute, influences of extraction, crosslinking, and paraffin swelling on the Payne effect of carbon black filled natural rubber nanocomposites are investigated systematically. Master curves of G′ as a function of γ could be always created, and overshoot of G″ in the filled vulcanizates weakens with increasing filler content and intensifies by dilution via paraffin swelling, suggesting that the Payne effect is not mainly rooted in the “filler network” and rubber-filler interfacial interactions. The filler reduces the onset strain amplitude of the Payne effect by amplifying microscopic strain amplitude of the rubber phase, irrespective of whether the matrix is crosslinked or not and whether the crosslinked matrix is swollen or not. Partial removal of bound rubber by compounding the paraffin swollen compounds could lower modulus and eliminate G″ overshoot of the deswollen vulcanizates without influence on the mechanism of G′ decay accompanying Payne effect. The overshoot is found to be closely related to the overall viscous characteristic of the vulcanizates in the linear viscoelastic regime. Provided herein are new insights for recognizing the important roles of the viscoelastic rubber phase on the Payne effect of the nanocomposites.