Relaxation Processes in Vulcanized Rubber. III. Relaxation at Large Strains and the Effect of Fillers

Abstract

Abstract Some experimental measurements are described of stress relaxation and creep at room temperatures in vulcanizates of natural rubber, butyl, and SBR. In an unfilled natural rubber vulcanizate the rate of stress relaxation is found to rise sharply for extensions of more than about 200%. Reasons are given for attributing this to the growth of a crystalline phase. Similar rates are observed at all extensions for a carbon black filled natural rubber vulcanizate. This is shown to be in satisfactory accord with the Mullins-Tobin model structure for filled vulcanizates, when the whole of the observed relaxation occurs in “softened” regions at rates appropriate to the high local deformations. The failure of rubber-carbon black associations with time does not appear to constitute a major relaxation process. In noncrystallizing unfilled vulcanizates the rate of relaxation is found to decrease somewhat with extension, possibly due to finite-extensibility effects. Preliminary measurements on a filled SBR vulcanizate suggest that a significant contribution to the observed relaxation arises from progressive failure of rubber-filler associations in this case. The relation derived previously between the rates of creep and stress relaxation at equivalent deformations is confirmed in all cases, within experimental error. Its validity in highly-irreversible systems is thus established experimentally.