
doi: 10.1007/bf00284070
Soluble fraction and equilibrium swelling in toluene were investigated on cis-1,4-polybutadiene networks being crosslinked in vacuo by 60Co-irradiation. Analysis of the sol fraction data by means of INOKUTI's equation reveals a drastic increase of the degradation-crosslink ratio for samples unpurified prior to crosslinking. Furthermore, the network crosslinking susceptibility depends on purification, although it is rather temperature insensitive for irradiation above the glass transition temperature of the rubber. The statistics of creation of crosslinks can be examined by suitable modification of INOKUTI's theory. From the present data it may be concluded that chain reaction crosslinking is negligible. The FLORY-REHNER formula for swelling equilibrium fails to reproduce the data at the cross link densities studied, but introducing a free end correction, the formula becomes applicable, with some over-correction. Hence the crosslink susceptibility could be obtained independently if the polymer-solvent heat interaction parameter were known. Additionally, the assumption about the proportionality of the crosslink density with radiation dose has been successfully tested by the swelling experiments.
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