We
consider the effects of concentration on the structural and rheological
properties of dilute polymer solutions via the use of Brownian
dynamics simulations. The model used here is that of Jendrejack
et al. [J. Chem. Phys.
116, 77527759 (2002)] for

-phage DNA
under good solvent conditions, which incorporates excluded volume and hydrodynamic
interaction effects, and has been shown to quantitatively predict the
nonequilibrium behavior of the molecule in the dilute limit. Our
work covers the entire dilute regime, with selected investigations into
the semidilute regime, as well as spanning multiple decades of
both shear and extensional flow rates. In simple shear flow,
as much as a 20% increase in chain extension and
30% increase in the reduced polymer viscosity is observed at
the overlap concentration, as compared to the infinitely dilute case.
Additionally, predicted shear viscosities are in very good agreement with
experimental observations. In elongational flow, we observe much stronger concentration
dependences than in shear, with a 110% increase in chain
extension and 500% increase in reduced viscosity when results are
compared at equivalent extension rates. Significant concentration effects are observed
at concentrations as low as 10% of the overlap concentration
and are largely the result of interchain hydrodynamic interactions.
©2006
The Society of Rheology