The rheological properties of aqueous polyurethane dispersions are reported
from the dilute regime up to mass concentrations in excess of 40 wt.%. Par
ticle size decreases and the particles are more resistant to shear induced
deformation with increasing ionic strength and, at very low ionic strength,
the reduced viscosity passes through a minimum with increasing concentrati
on. As the mass fraction of polyurethane increases, the dispersions shear t
hin. The zero shear rate viscosity diverges with the development of an appa
rent yield stress at the highest concentrations probed. Stress sweep experi
ments show that deviation from linear viscoelasticity occurs at strains of
less than 0.05% for the moderately concentrated dispersions. The Cox-Merz r
ule is obeyed by these dispersions only at strains in the linear viscoelast
ic region and at concentrations below the gel point. As the ionic strength
is increased at fixed particle concentration, viscosities pass through a mi
nimum. These phenomena are discussed in terms of particle deformability and
an interplay of electrostatic and steric repulsive forces. (C)1999 Elsevie
r Science B.V. All rights reserved.