On the significance of molecular surfaces and thermodynamic interactions for the excess viscosities of liquid mixtures

The viscosities η of homogeneous binary mixtures of liquids are usually approximated as In η = ϕ1 In η1 + ϕ2 In η2 where ϕi and ηi are the volume fractions and the viscosities, resp., of the i-th pure substance; the behavior of real systems is then discussed in terms of Δ In η, the deviations from the above reference behavior. Here a semi-empirical approach is presented according to which volume fractions are replaced by the surface fractions Ωi to create a more realistic reference state, and the thermodynamic interaction parameter g is taken into account. The new equation reads (expressing it for practical purposes still in the terms of ϕi) γ is a geometric factor, measuring the difference…

The viscosities of moderately concentrated solutions of poly(butyl methacrylate)—Mw = 1820 kg/mol–in the thermodynamically good solvent toluene and in the theta solvent 2-propanol were measured up to pressures of 2000 bar as a function of shear rate in the temperature interval from 40 to 70°C. Both systems obey Graessley's equation so that it is possible to obtain the following rheological parameters in addition to the zero-shear viscosity η0 from the dependences . η can be split into an entanglement part ηent plus a frictional contribution ηfric, and the characteristic viscometric relaxation time τ0 becomes accessible. The present results demonstrate that the application of pressure raises…