Tuesday, 1 November 2005 - 4:45 PM
283g

A Gaussian Slip-Link Model for Cross-Linked Polymers

Mahnaz Eskandari, Jay D. Schieber, and Hamid Arastoopour. Chemical Engineering, Illinois Institute of Technology, Suite 127, 10 W. 33rd street, Chicago, IL 60616

Simulating the molecular structure of cross-linked polymers has difficulties mainly caused by the heterogeneous distribution of the cross-links; the presence of entanglements; and the displacement of both entanglements and cross-links under deformation. We have developed a slip-link model with cross-links, which are deformed affinely at the equilibrium, and assuming Gaussian chains neglecting the presence of chain segments not in the network. Simulation consists of two steps: preparation and deformation. In the preparation step, cross-links and slip-links are assumed to be distributed uniformly along the chain, but with independent parameters describing their statistics: the average number of Kuhn steps between entanglements,Ne, and the average number of Kuhn steps between cross-links,Nc . The dynamic variables include the number of Kuhn steps for the slip-link strands and the slip-link strand vector. In the second step, the variables of the preparation step become the parameters of the deformation step and the stress tensor can be found as a function of the deformation. The Mooney plot of the simulation result has a good agreement with experimental data for uni-axial and equibiaxial elongation deformations for cross-linked natural rubber, poly(dimethyl-siloxane), and poly(butadiene). The model is used to predict values for the Mooney plot parameters (C1 and C2) as a function of Ne and the average number of the slip-link strands < z > . The average number of the slip-link strands < z > is proportional to Nc / Ne ratio. The C2 / C1 ratio is found to be strongly dependent on < z > , but weakly dependent on Ne. From the experimental data for a given cross-linked polymer, this observation provides a new way of predicting the cross-link density and separating it from the entanglement density. However, for systems of known Ne (from the plateau modulus for the melt or the Cornet criterion) and known cross-link density (such as calorimetry experiments), the model requires no adjustable parameters. The model has been tested also for planar elongation deformation of poly(dimethyl-siloxane) and it captures the first and second normal difference stresses in comparing with the experimental data.

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