Journal of Polymer Science Part B: Polymer Physics, Vol.36, No.1, 181-190, 1998
The effect of concentration, temperature, and molecular weight on the dynamics of rigid-rod molecules in semi-dilute solutions
The dynamics of rigid-rod-like molecules are studied using rheo-optical techniques. Measurements of flow birefringence as a function of shear rate are utilized to understand the scaling behavior of rotational diffusivity with respect to concentration and temperature. The concentration scaling exponent increases with increasing concentration and the scaling laws are valid in narrow concentration windows. The Doi-Edwards (DE) scaling law D-r similar to c(-2), holds at very high concentrations (cL(3) > 150). The concentration scaling exponent decreases dramatically with increasing temperature at concentrations, cL(2)d > 1. Scaling of rotational diffusivity, with respect to temperature and solvent viscosity in the semidilute regime, does not follow the predictions of DE theory (and related caging ideas). On the contrary, a model proposed by Fixman was found to explain both the temperature and concentration dependence of the rotational diffusivity.
Keywords:SEMIDILUTE POLYMER RODS;TRANSIENT SHEAR-FLOW;RODLIKE POLYMERS;NONDILUTE SOLUTIONS;RHEOOPTICAL RESPONSE;BROWNIAN DYNAMICS;COLLAGEN PROTEIN;MACROMOLECULES