Elastic properties of nonstoichiometric reacted PDMS networks

The influence of stoichiometry on the elastic modulus of eight-functional end-linked poly(dimethylsiloxane) (PDMS) networks was investigated by extensional rheometry with extensions up to more than 100%, and the stress-strain relation was found to be almost linear-a characteristic property for a network structure with an eight-functional cross-linker. The experimental data were compared to a stochastic model taking into account entanglements and to Monte Carlo simulations. The Mooney-Rivlin model was furthermore used to fit the data, and the dependency of C-1 and C-2 parameters on the stoichiometric ratio was investigated in order to clarify especially the influence of trapped entanglements acting either as chemical cross-links or as sliding links. It was found that including a locking factor dividing trapped entanglements into locked entanglements and slip-links could explain our data obtained for the Mooney-Rivlin constants. It was furthermore found that trapped entanglements dominate when there is an excess of cross-linker, ensuring that all long difunctional DMS chains are bound to the infinite network in both ends.