Abstract
Abstract Experimental results indicate that the socalled “cold flow” of polysulfide rubbers is almost certainly chemical rather than physical in nature. The term chemorheology has been adopted to describe this chemical type of plasticity. The experimental method employed in this investigation was the measurement of relaxation of stress in stretched rubber samples held at a constant elongation. The changes in relaxation rate produced by changing the molecular structure of the rubber (by cross-linking), by incorporating carbon black, by illuminating with ultraviolet light, and by treating the rubber with various chemical agents, such as sulfur, a thiol, and agents that destroy thiol groups, were studied by this method. From the results of the above experiments and from additional considerations, it is concluded that the chemical reaction responsible for cold flow is an intermolecular exchange reaction, and that this exchange reaction is probably an exchange between a terminal thiol group of one chain and a disulfide linkage of an adjacent chain.
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