On the scaling of molecular weight distribution functionals

When formulating a constitutive equation model or a mixing rule for some synthetic or biological polymer, one is essentially solving an inverse problem. However, the data will not only include the results obtained from simple step strain, oscillatory shear, elongational, and other experiments, but also information about the molecular weight scaling of key rheological parameters (i.e., molecular weight distribution functionals) such as zero-shear viscosity, steady-state compliance, and the normal stress differences. In terms of incorporating such scaling information into the formulation of models, there is a need to understand the relationship between various models and their molecular weight scaling, since such information identifies the ways in which molecular weight scaling constrains the choice of possible models. In Anderssen and Mead (1998) it was established formally that the members of a quite general class of reptation mixing rules all had the same molecular weight scaling. The purpose of this pa per is to first introduce the concept of a generalized reptation mixing rule, which greatly extends the class examined by Anderssen and Mead, and then show that all such rules have the same molecular weight scaling. The proof is similar to that given by Anderssen and Mead, but uses the implicit function theorem to establish the uniqueness of the mean values which arise when invoking various integral mean-value representations for the molecular weight distribution functionals considered. The rheological significance of the new generalized two-parameter mixing rule, proposed in this paper, is examined in some detail in the conclusions. In particular, it is used to established how one must construct a mixing rule for a general polydispersed polymer where the molecular dynamics involves some single, some double and some higher levels of multiple reptation. The work of Maier et al. (1998) and Thimm et al. (2000) is then utilized to illustrate and validate this proposal.