Springer Online Journal Archives 1860-2000
Chemistry and Pharmacology
Abstract A mathematical model based on the diffusion-convection equations is used to describe the rheological properties of dilute polymer solutions. The model uses a second-order conformation tensor as a measure of the internal strain; this avoids the mathematical complexity resulting from the use of a more detailed description of the macromolecules and also avoids the necessity of introducing additional ad-hoc assumptions (closure approximations) commonly used in other molecular theories. The rheological equation is obtained in terms of the rate-of-deformation tensor $$\dot \gamma $$ and a scalar functionf(σ) relating the extra stress tensorσ to the internal strain tensorc. The functionf(σ) depends on the physical insight introduced in the Helmholtz free energyA(c) of the solvent-polymer system. This approach is illustrated for an intra-molecular potential of a “FENE-charged” type. The concept of an isotropic, but conformation-dependent, friction coefficient, is also introduced to account for the “coil-stretch” transformation of macromolecules in solution. Viscosity and first normal-stress data, of partially hydrolyzed polyacrylamide solutions, (polyelectrolytes) are analyzed and compared to the model predictions in steady shear and elongational flows.
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