The fatigue ageing of vulcanised rubbers

The cause of the respective rough and smooth fatigue failure surfaces of Neoprene GS : Neoprene W and Neoprene GS : natural rubber vulcanisates is investigated. The contrasting morphology of the vulcanisates is found to be the major factor determining the fatigue behaviour of the blends. Neoprene GS and Neoprene W appear to form homogeneous blends which exhibit physical properties and fatigue failure surfaces intermediate between those of the two horropolymers. Neoprene GS and natural rubber exhibit heterogeneity when blended together. The morphology of these blends is found to influence both the fatigue resistance and failure surface of the vulcanisates. Exceptional uncut and cut initiated fatigue lives are observed for blends having an interconnecting network morphology. The network structure and cross-link density of the elastomers in the blends and the addition of carbon black and antioxidant are all found to influence the fatigue resistance but not the failure mechanism of the vulcanisate.

Fatigue in rubber vulcanisates

A study has been made of the effect of single extensions and continuous fatigue on the structures of various natural rubber networks. The change in network structure of a conventional vulcanisate on a single extension manifests itself as permanent set. The change in network structure has been assessed by the use of the chemical probes, propan-2-thiol/piperidine, hexane-thiol/piperidine and triphenyl phosphine, which determine the polysulphide and disulphide crosslink densities and main chain modification respectively. The permanent set induced on a single extension of a conventional sulphur vulcanisate has been shown to result from the destruction and reformation of polysulphide crosslinks. The magnitude of the effect was dependent upon the degree of extension and showed a maximum at extensions corresponding to the onset of stress-induced crystallisation. The incorporation of a reinforcing filler, HAF-carbon black, magnified the effect. Vulcanisates that possessed only mono and disulphide crosslinks did not show any significant permanent set. The continuous changes in network structure during fatigue have also been determined, and the effects of carbon black and antioxidants on these changes and the fatigue life have been assessed. During fatigue the overall crosslink density increased slightly, which resulted from the destruction of polysulphide crosslinks. and their replacement by principally disulphide crosslinks. Antioxidants reduced the rate of destruction of polysulphide crosslinks and increased the fatigue life of the rubber network. The fatigue life of the network also depended upon the concentration of free chain ends. These chain ends were incorporated into the network by masticating rubber under nitrogen in the presence of bis (diisopropyl)thiophosphoryl disulphide, which improved the fatigue resistance by up to 9%.