The chain end distributions and crosslink characteristics in black-filled rubbers

A black-filled rubber compound consists of two phases: the free polymer phase, where no particle exists, and the carbon black agglomerate phase, where highly concentrated particles are bound by a small amount of the polymer-so called bound rubber. The Charlesby-Pinner virtual linear number-average molecular weight Mn-1 ol the polymer in each phase is determined for black-filled compounds to obtain information about the chain end distribution in the compounds. The nominal crosslink density of the bound rubber is also measured by means of the swelling measurement of the "carbon gel" to characterize the crosslink variation in the vulcanizates. The results indicate that the chain end density is much higher in the agglomerate phase than in the free polymer phase due to enhanced chain scission during mixing. The enhancement of scission is considered due to the free radical crosslinking which imposes restriction to chain slippage in the flow field. This together with the previous findings suggests the features of the phase construction in the filled vulcanizates: tightly crosslinked free polymer phase with fewer chain ends, and loosely crosslinked agglomerate phase with more chain ends but, with rather suppressed chain mobility due to the dense nano-scale particles. The features match well with the energy dissipating and the toughened nature of the filled vulcanizates.