Macromolecules, Vol.32, No.4, 1212-1217, 1999
Correlation length and entanglement spacing in concentrated hydrogenated polybutadiene solutions
The concentration correlation length, xi, and the entanglement spacing, d, have been determined in solutions of hydrogenated polybutadiene in n-alkane solvents at 140 degrees C by small-angle neutron scattering and rheology, respectively. The Former varies as xi similar to phi(-0.76) over the range 0.04 < phi < 0.7. This result is in agreement with scaling predictions for semidilute solutions in a good solvent, but interestingly this dependence extends to concentrations well beyond the regime where the scaling law should be valid. The entanglement spacing was obtained via measurements of the dynamic loss modulus, G ", as a function of frequency, omega, from phi = 0.2 to phi = 1. The maximum value of G " in the terminal dispersion regime varies as phi(1.9), implying that d similar to phi(-0.45). The shape of G "(omega) was independent of phi and M, and d was independent of M, as expected for well-entangled solutions. These results indicate that the entanglement spacing and the correlation length need not have the same concentration dependence in concentrated solutions in a good solvent. The ratio xi/d, termed the constraint porosity parameter in the polymer mode-coupling theory, varies from 0.09 in the melt to 0.15 when phi = 0.2, which may have important implications for the concentration dependence of the molecular weight exponent for chain diffusion.
Keywords:MODE-COUPLING THEORY;VISCOELASTIC PROPERTIES;LINEARPOLYSTYRENE;MOLECULAR-WEIGHT;TRACER-DIFFUSION;SELF-DIFFUSION;POLYMERS;DYNAMICS;CHAIN;COEFFICIENT