Rubber—Black Interaction Influence on Cure Level of Vulcanizates

Abstract

Abstract The crosslink density of vulcanizates has been quantitatively investigated using swelling measurements (Vr) of compounds of cis-1,4-polybutadiene reinforced with N242, N326, or N990 (Vulcan 6H, Regal 300, Sterling MT). Crosslink density in both filled and unfilled stocks is shown to be related to the molar concentration of the curatives in the unbound rubber phase of the vulcanizates and not merely to total concentration. The effects of different carbon black loadings and of cure time are demonstrated to be fully describable by the extent of carbon black—rubber interaction, measured by bound rubber; that occurs during mixing and during the induction period of the cure step. Greater rubber-black interaction, whether achieved by higher black level or from higher reinforcing blacks, always yielded vulcanizates of increased crosslink density compared to an identically vulcanized gum control. Calculating curative concentration on the basis of unbound rubber—rather than total rubber—illustrated the expected dependence of crosslink density upon curative concentration and graphically explains the presence of so-called “excess” crosslinks. Implied, also, is one cause for the “scorchy” character of highly reinforcing blacks and the higher modulus obtained with these blacks.