Abstract

Networks were prepared in the swollen and dry states to investigate the influence of physical relaxation on chemical stress–relaxation. The stress–relaxation behavior of solution-cured samples was different significantly from that of the samples crosslinked conventionally. The same result was also observed in the number of chain scission for both kinds of samples. On the other hand, the number of chain scission estimated by using the swelling method for samples crosslinked conventionally was in good agreement with that by the chemical stress–relaxation for solution-cured samples. It was found that there is little or no influence of the physical relaxation caused by entanglements, and no effect of dangling chains arising from scission in the equilibrium swelling. The relative change of network chain density determined by means of the swelling method was also consistent with that by sol fraction determination. These results indicate that the swelling method can be used as a measure of a degree of degradation on chemorheology. Taking into account the influence of physical relaxation on chemical stress–relaxation, a new relationship between the relative stress decay and the relative network chain density was experimentally proposed.

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