DEPENDENCE OF THE MODULI OF RANDOM BIMODAL NETWORKS ON CHAIN-LENGTH DISTRIBUTION

There have now been a number of experimental studies on the preparation and elastomeric properties of random bimodal networks of polydimethylsiloxane. The mole per cent of the short chains and their molecular masses covered a wide range, thus resulting in various polydisperse chain-length distributions. The networks were studied with regard to their stress-strain isotherms in elongation, and values of their moduli in the large-deformation (phantom) limit were found to depend on the chain-length distribution. This important result is in disagreement with phantom network theory, which assumes the elastic modulus is dependent only on the mean value of chain lengths such that the cycle rank of the network is preserved. The effective functionality of the long chains was found to depend on the number of short chains present. Better agreement with experiment was obtained when account was taken of the connectivity of the very short chains, in what is essentially a bimodal distribution of both network chain lengths and cross-link functionalities. Relevant here is the fact that as the degree of chemical cross-linking increases, the shear modulus G moves away from the affine limit, toward the phantom limit. This increase toward phantom behavior is presumably due to the fact that the mutual interspersion of chains is less when the chains are shorter, even in the small-strain region.