Mechanistic modeling of reversion phenomenon in sulphur cured natural rubber vulcanization kinetics

A novel kinetic model of natural rubber sulphur vulcanization is proposed. The modeling approach takes into account current knowledge on the different polysulfidic structures present during vulcanization, and the associated individual reactions. A simplified scheme is proposed, giving a mechanistic view of the reversion phenomenon, which results in a decrease of the elastic modulus (related to the sulphur crosslink density) for long vulcanization times at high temperature. The resulting set of differential equations is solved by an appropriate numerical method to predict the evolution of the degree of vulcanization for isothermal cure conditions. The vulcanization kinetics of a model natural rubber compound was characterized experimentally by rheological measurements, in order to test the proposed kinetic model. A remarkable agreement between model predictions and experimental data is observed. The identified kinetic parameters corresponding to the individual reactions taken into account by the mechanistic model are consistent with those of an existing, less refined, pseudo-mechanistic model. The proposed model thus allows bridging the gap between the prediction of macroscopic variations of the elastic modulus and the evolution of molecular scale structure during vulcanization when the reversion phenomenon is present.