Electroviscous effect of concentrated suspensions in salt-free media: Water dissociation and CO2 influence

The electroviscous effect of realistic salt-free colloidal suspensions is analyzed theoretically. We study the influence on the electroviscous coefficient of the surface charge density and the particle volume fraction. By realistic salt-free colloidal suspensions we mean aqueous suspensions which have been deionized as far as possible without any electrolyte added during the preparation, in which the only ions present can be (i) the so-called added counterions, coming from the ionization of surface groups and thus counterbalancing the surface charge, (ii) the H+ and OH− ions from water dissociation, and (iii) the ions produced by the atmospheric CO2 contamination. Our model is elaborated in the framework of a classical mean-field theory, using the spherical cell model approach and the appropriate local equilibrium reactions. It is valid for arbitrary surface charge density and particle concentrations. We have also made a new interpretation of the electroviscous coefficient: the electroviscous coefficient p of the suspension is the ratio between the electrohydrodynamic and the pure hydrodynamic contributions to the specific viscosity of the suspension. The numerical results show that it is necessary to consider the water dissociation influence for volume fractions lower than approximately 10−3, whereas the atmospheric contamination, if the suspensions are open to the atmosphere, is important in the region of volume fractions ϕ < 0.03.