Some Aspects of High Temperature Vulcanization

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Abstract
When a thin rubber sample is heated to a high curing temperature, the initial kinetics of cure as derived from Newton's rule can be represented by a well-defined time delay at the final curing temperature. This facilitates quantitative studies for which it is also shown that first order changes in crosslink density can be assessed by modulus measurements. The vulcanization rate constants thus determined in the case of a polychloroprene compound indicate the apparently different action of the vulcanization accelerator at conventional and at high temperatures, which allows a fundamental interpretation to be advanced. Partial reversion at high temperature is shown for both the ACS1 and a thiuram-cured natural rubber compound, and using an appropriate graphical method, vulcanization and reversion can be evaluated as first order processes. Two simple overall reaction schemes are developed to fit the experimental data with only three calculated rate constants. Quinoid and peroxide curing systems are also examined.

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