Solid-state C-13 NMR studies of vulcanized elastomers - XVII. Effect of carbon black grade on the network structure in natural rubber vulcanizates

The vulcanization chemistry and network formation of carbon black filled natural rubber vulcanized with sulfur and TBBS were studied using solid-state C-13 NMR and equilibrium swelling measurements. A reduction in the sulfur rank of the A1 type sulfide and increased production of B1 type polysulfide are observed when the carbon black concentration increases in natural rubber. At the same loading level, the structural property or grade of carbon black does not affect qualitatively the type of sulfide formation. The efficiency of the intermolecular crosslinking over the whole range of sulfurizations is 45.7% for the unfilled vulcanizate. The extent of the chemical sulfurization reactions (NMR result) is constant with black incorporation, while the total network (swelling result) increases with increases in the black loading. The amount of physical entanglements, estimated from the comparison of the NMR and swelling results, is found to increase linearly with the carbon black concentration. The entanglements increase as a function of the 300% modulus, which suggests that the effective level of reinforcement depends on the nature of the individual carbon black. It is assumed that physical adsorption plays a major role in the polymer-filler interactions in the natural rubber/carbon black system.