Degraded rubber vulcanizates swollen in benzene was cooled, and the degree of freezing point depression of the benzene,
ΔT, was determined. This measurement is generally called a cryoscopic method. It was experimentally found that the relationship between
ΔT and the average radius of gyration of network chains, RG, which characterizes mesh size of network in swollen crosslinked rubber, can be given by the following equation :
ΔT-R
GmThe above relation is the same as those of an undegraded rubber vulcanizates, except for the numerical coefficient. The exponent m of degraded networks was larger than that of undegraded ones.
ΔT increases due to smaller meshes remaining in degraded networks, even if the crosslink density of a degraded sample is equal to that of an undegraded one. Meshes of various size exist in degraded networks and the distribution of mesh size occurs, which is influenced by degradation conditions and/or degradation mechanism, and the exponent m can reflect the inhomogeneity of degraded network structure. Such the inhomogeneity can be detected only by a cryoscopic method, but not by the conventional technique such as stress-strain measurement and the swelling method.
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