The Dispersion of Carbon Black in Rubber Part III. The Effect of Dispersion Quality on the Dynamic Mechanical Properties of Filled Natural Rubber

The Part I of this series described a rapid method for determining the quality of carbon-black dispersion. The second paper (Part II) was concerned with the kinetics of the dispersion of carbon black into natural rubber (dispersion quality as a function of mixing time) in an internal mixer. In this paper we consider the effects of changes in dispersion quality on the dynamic mechanical properties of both unvulcanized and vulcanized natural rubber. The effects of changes in the degree of carbon-black dispersion were measured by using a new prototype moving-die rheometer (which is presently being developed at Monsanto Instruments & Equipment Research Laboratory). By using this prototype rheometer, G′ and G″ were measured as functions of shear-strain amplitude, temperature, and frequency. Increases in the degree of carbon-black dispersion in uncured natural rubber (starting from very poor dispersion quality) give decreases in the values of both G′ and G″. The decrease in dynamic moduli with increases in the degree of carbon-black dispersion might be explained on the basis of a network of agglomerates which exists when the quality of dispersion is extremely poor. In the case of uncured samples, values of G′, measured at low strains (e.g. ±1%), become reduced after the imposition of a larger (±50%) sinusoidal shear strain for a short period of time (e.g. 3 s). Then, with the passage of time, the reduced value of G′ partially recovers. The extent of this recovery increases with increases in the dispersion rating DR. Similar results were obtained with respect to the loss modulus G″. In both cases, the extent of recovery is much less when the carbon black is very poorly dispersed. The unrecoverable proportion of G′ or G″ is also considered to be due to a network composed of mutually interactive agglomerates of carbon black.