Model networks of end-linked polydimethylsiloxane chains. VII. Networks designed to demonstrate non-Gaussian effects related to limited chain extensibility

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Abstract
End‐linking polymer chains by means of a multifunctional cross‐linking agent provides an ideal way for obtaining elastomeric networks of any desired distribution of chain lengths. In the present investigation, this technique was employed to give polydimethylsiloxane networks consisting of various proportions of relatively long and very short network chains. The stress–strain isotherms of these networks generally showed an anomalous increase in the modulus at high elongation, and the increase persisted at high temperatures and high degrees of swelling. This non‐Gaussian effect was quantitatively correlated with the limited extensibility of the network chains; specifcally, the increase in modulus was found to begin at approximately 60%–70% of the maximum extensibility of the network chains, and network rupture at 80%–90%. The elongation at which the increase becomes evident increases with decrease in the proportion of the very short chains, thus verifying the nonaffine nature of the deformation at high elongation. In addition, the elasticity constants characterizing the Gaussian regions of the isotherms, and the values of the degree of equilibrium swelling were used to evaluate the most recent molecular theories of rubberlike elasticity, particularly with regard to the structure factor relating the modulus of an elastomer to the average length or molecular weight of the network chains.