The reinforcement and concomitant nonlinear viscoelastic behavior have been investigated for several composites of linear polymer melt with various binary mixtures of nanofillers having different surface chemistries and particle sizes. The dependence of storage modulus and loss factor on dynamic shear strain amplitude has been obtained for several compositions of each binary filler pair. Composites with mixed fillers display nonlinear interactions that are filler pair/matrix specific. Total filler concentration appears to be a major factor, suggesting that nearest neighbor particle spacing is crucial even if the neighbors are of a different filler type. The results are consistent with the theory recently proposed by Sternstein and Zhu in which the high reinforcement by nanofillers is due to the trapping of entanglements and the resultant effects on matrix chain mobility and entropic elasticity. At high strain amplitudes, the storage modulus and loss factor of the composites with binary filler mixtures are found to be nearly independent of the filler mixture ratio, and dependent only on the total filler concentration. A “partial molar” storage modulus for mixed filler composites is defined for future considerations, and specific interactions are presented for two binary filler systems.

The Two Coupled Maxwell Modes (TCMM)Model is applied to give quantitative descriptions of shearthickening behavior, which can be observed under certain conditions for high molecular weight polymers dissolved in low viscosity solvents. The TCMM Model is written in terms of five parameters representing the relaxation time of each mode, the concentration of each mode, and a coupling parameter between the two modes. Using all of the available experimental data for steady-shear viscosity and dichroism we found in the literature, we performed a full parameterization of these five quantities. Furthermore, from this parameterization we can describe the functional dependencies of the relaxation times, modal concentrations, and coupling parameter as functions of temperature, concentration, and molecular weight of the polymer. These functional dependencies are explained in light of the underlying physics imbedded in the TCMM Model. We demonstrate that by optimizing to only the viscosity data, we were able to obtain the same relaxation times, modal concentrations, and coupling parameter as using both the viscosity and dichroism data. This is useful because typically the experimental dichroism data is not available.

The microscopic origins of five rheological models are investigated by comparing their predictions for the conformation tensor and stress tensor with the same tensors obtained via nonequilibrium molecular dynamics simulations for n-hexadecane. Steady-state simulations were performed under both planar Couette and planar elongational flows, and the results of each are compared with rheological model predictions in the same flows, without any fitting parameters where possible. The use of the conformation tensor for comparisons between theory and experiment/simulation, rather than just the stress tensor, allows additional information to be obtained regarding the physical basis of each model examined herein. The character of the relationship between stress and conformation is examined using model predictions and simulation data.

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