Mullins Effect and Crack Growth in Natural Rubber Vulcanizates during Heat Aging and Cyclic Loading

Abstract

The effect of thermal aging and cyclic loading on mechanical properties and development of cracks in natural rubber vulcanizates was studied. After aging at 70oC and 110oC vulcanizates were subjected to cyclic loading. At a certain number of loading cycles, the samples were conducted in a tension test. At the aging condition of 70oC, the static tensile properties of material stay almost unchanged even after 88 aged hours and 8000 loading cycles. On the contrary, the dynamic fatigue resistance of vulcanizates decreases with increasing aging time. These results are attributed to the post-curing and the development of microcracks that might be caused by Mullins effect: in the case of static loading, the strain-induced crystallization may prevent cracks growth, but in the case of cyclic loading the strain-induced crystallization does not occur, so cracks develop without hindrance. However, at 110oC both static properties and dynamic fatigue resistance of material reduced dramatically because at high temperature the heat degradation exceeds both post-curing and strain-induced crystallization. Crack formation and propagation were examined by a digital optical microscope in the progress of cyclic loading. Results showed that natural rubber vulcanizate filled with carbon black has the best crack growth resistance (CGR) while the addition of modified and unmodified silica reduces CGR of materials. Moreover, the vulcanizate with unmodified silica has the lowest CGR.