The rheology of polymeric liquid crystals

The molecular theory of Doi has been used as a framework to characterize the rheological behavior of polymeric liquid crystals at the low deformation rates for which it was derived, and an appropriate extension for high deformation rates is presented. The essential physics behind the Doi formulation has, however, been retained in its entirety. The resulting four-parameter equation enables prediction of the shearing behavior at low and high deformation rates, of the stress in extensional flows, of the isotropic-anisotropic phase transition and of the molecular orientation. Extensional data over nearly three decades of elongation rate (10^–2–10¹) and shearing data over six decades of shear rate (10^–2–10⁴) have been correlated using this analysis. Experimental data are presented for both homogeneous and inhomogeneous shearing stress fields. For the latter, a 20-fold range of capillary tube diameters has been employed and no effects of system geometry or the inhomogeneity of the flow-field are observed. Such an independence of the rheological properties from these effects does not occur for low molecular weight liquid crystals and this is, perhaps, the first time this has been reported for polymeric lyotropic liquid crystals; the physical basis for this major difference is discussed briefly. A Semi-empirical constant in eq. (18), N/m² - c rod concentration, rods/m³ - c ^* critical rod concentration at which the isotropic phase becomes unstable, rods/m³ - C interaction potential in the Doi theory defined in eq. (3) - d rod diameter, m - D semi-empirical constant in eq. (19), s^–1 - D _r lumped rotational diffusivity defined in eq. (4), s^–1 - rotational diffusivity of rods in a concentrated (liquid crystalline) system, s^–1 - D _ro rotational diffusivity of a dilute solution of rods, s^–1 - f distribution function defining rod orientation - F tensorial term in the Doi theory defined in eq. (7) (or eq. (19)), s^–1 - G tensorial term in the Doi theory defined in eq. (8) - K _B Boltzmann constant, 1.38 × 10^–23 J/K-molecule - L rod length, m - S scalar order parameter - S tensor order parameter defined in eq. (5) - t time, s - T absolute temperature, K - u unit vector describing the orientation of an individual rod - rate of change ofu due to macroscopic flow, s^–1 - v fluid velocity vector, m/s - v velocity gradient tensor defined in eq. (9), s^–1 - V mean field (aligning) potential defined in eq. (2) - x coordinate direction, m - Kronecker delta (= 0 if = 1 if = ) - _r ratio of viscosity of suspension to that of the solvent at the same shear stress - _s solvent viscosity, Pa · s - ^* viscosity at the critical concentrationc ^*, Pa · s - v ₁, v₂ numerical factors in eqs. (3) and (4), respectively - deviatoric stress tensor, N/m² - volume fraction of rods - ⁰ constant in eq. (16) - ^* volume fraction of rods at the critical concentrationc ^* - average over the distribution functionf(u, t) (= d ²u f(u, t)) - gradient operator - d ²u integral over the surface of the sphere (|u| = 1)